JP2021178802A - Organic silicon compound - Google Patents
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- 150000003377 silicon compounds Chemical class 0.000 title abstract description 8
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 claims abstract description 51
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 8
- 229920006136 organohydrogenpolysiloxane Polymers 0.000 claims abstract description 8
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 32
- -1 hydrogen siloxane Chemical class 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 12
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 claims description 4
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 claims description 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 13
- 238000004132 cross linking Methods 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- 239000003431 cross linking reagent Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000007259 addition reaction Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 0 *C(C1(C(*)=C(*)C1(*)C12*)C1=*)C2(*)C=C Chemical compound *C(C1(C(*)=C(*)C1(*)C12*)C1=*)C2(*)C=C 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- KWEKXPWNFQBJAY-UHFFFAOYSA-N (dimethyl-$l^{3}-silanyl)oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)C KWEKXPWNFQBJAY-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 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
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RCNRJBWHLARWRP-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane;platinum Chemical compound [Pt].C=C[Si](C)(C)O[Si](C)(C)C=C RCNRJBWHLARWRP-UHFFFAOYSA-N 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
本発明は、有機ケイ素化合物に関する。詳述には、１分子中にノルボルネン構造とヒドロシリル基を有する有機ケイ素化合物に関する。 The present invention relates to organosilicon compounds. More specifically, the present invention relates to an organosilicon compound having a norbornene structure and a hydrosilyl group in one molecule.
ヒドロシランはＳｉ−Ｈ結合を持ち、金属触媒の存在下、不飽和基と付加反応することができるためシリコーン分野の各種合成や、室温硬化型シリコーンゴムの架橋反応などに利用されている（特許文献１）。 Since hydrosilane has a Si—H bond and can undergo an addition reaction with an unsaturated group in the presence of a metal catalyst, it is used for various synthesis in the field of silicone and for cross-linking reaction of room temperature curable silicone rubber (Patent Documents). 1).
また、１分子中に不飽和基とＳｉ−Ｈ（ヒドロシリル基）結合双方を持つシランとしては、特許文献２にヒドロシリル化反応可能な炭素−炭素不飽和基とヒドロシリル基とを分子内に共有するポリシロキサンが開示されており、該ポリシロキサンと、ヒドロシリル化触媒と、好ましくは炭素−炭素三重結合を有する基がケイ素原子に結合している構造を持つ安定剤、とを含む硬化性組成物は保存安定性に優れており、組成物の硬化物が耐熱性に優れることが開示されている。 Further, as a silane having both an unsaturated group and a Si—H (hydrosilyl group) bond in one molecule, the carbon-carbon unsaturated group and the hydrosilyl group capable of hydrosilylation reaction are shared in the molecule in Patent Document 2. Polysiloxane is disclosed, wherein a curable composition comprising the polysiloxane, a hydrosilylation catalyst, and preferably a stabilizer having a structure in which a group having a carbon-carbon triple bond is bonded to a silicon atom. It is disclosed that the cured product of the composition is excellent in heat resistance and is excellent in storage stability.
しかしながら、１分子中に不飽和基とＳｉ−Ｈ（ヒドロシリル基）結合双方を持つシランは少なく、特にノルボルネン構造をもつものは知られていない。 However, there are few silanes having both unsaturated groups and Si—H (hydrosilyl group) bonds in one molecule, and especially those having a norbornene structure are not known.
ノルボルネン構造中の内部不飽和基は立体障害の問題でビニリデン部よりも反応性が悪いことが知られている。したがって、１分子中に内部不飽和基とヒドロシリル基双方を持つシランは、該ヒドロシリル基が他分子中のヒドロシリル化反応可能な不飽和基と反応しても、ノルボルネン構造中の内部不飽和基はヒドロシリル化に関与しないため、該内部不飽和基を分子中に残すことができると考えられる。 It is known that the internal unsaturated group in the norbornene structure is less reactive than the vinylidene moiety due to the problem of steric hindrance. Therefore, in a silane having both an internal unsaturated group and a hydrosilyl group in one molecule, even if the hydrosilyl group reacts with an unsaturated group capable of hydrosilylation in another molecule, the internal unsaturated group in the norbornene structure remains. Since it does not participate in hydrosilylation, it is considered that the internal unsaturated group can be left in the molecule.
本発明は、１分子中にノルボルネン構造とヒドロシリル基の両方を有する有機ケイ素化合物を提供することを目的とする。 An object of the present invention is to provide an organosilicon compound having both a norbornene structure and a hydrosilyl group in one molecule.
本発明は、上記目的を達成するためになされたものであり、１分子中にノルボルネン構造とヒドロシリル基を有する有機ケイ素化合物であって、
下記一般式（１）で表されるノルボルネン構造含有オルガノハイドロジェンポリシロキサンである有機ケイ素化合物を提供する。
Provided is an organosilicon compound which is a norbornene structure-containing organohydrogenpolysiloxane represented by the following general formula (1).
このような有機ケイ素化合物は、１分子中にノルボルネン構造とヒドロシリル基の両方を有する有機ケイ素化合物である。このような有機ケイ素化合物は、白金触媒存在下、他分子中の各種のヒドロシリル化反応可能な不飽和基と反応させることができ、かつヒドロシリル化に関与しないノルボルネン構造中の内部不飽和基を残すことができるため、架橋剤として有用である。 Such an organosilicon compound is an organosilicon compound having both a norbornene structure and a hydrosilyl group in one molecule. Such organosilicon compounds can react with various hydrosilylation-reactive unsaturated groups in other molecules in the presence of platinum catalysts, leaving internal unsaturated groups in the norbornene structure that are not involved in hydrosilylation. It is useful as a cross-linking agent because it can be used.
また、本発明は、１分子中にノルボルネン構造とヒドロシリル基を有する有機ケイ素化合物の製造方法であって、
ノルボルネン構造を有する化合物とヒドロシリル基を有する化合物をヒドロシリル化反応させることで、ノルボルネン構造含有中間体を合成し、
該ノルボルネン構造含有中間体を下記一般式（２）で表されるハイドロジェンシロキサンと酸平衡させることで、下記一般式（１）で表されるノルボルネン構造含有オルガノハイドロジェンポリシロキサンを製造する有機ケイ素化合物の製造方法を提供する。
By hydrosilylating a compound having a norbornene structure and a compound having a hydrosilyl group, a norbornene structure-containing intermediate is synthesized.
Organosilicon for producing a norbornene structure-containing organohydrogenpolysiloxane represented by the following general formula (1) by acid equilibrating the norbornene structure-containing intermediate with a hydrogen siloxane represented by the following general formula (2). A method for producing a compound is provided.
このような有機ケイ素化合物の製造方法であれば、１分子中にノルボルネン構造とヒドロシリル基の両方を有する有機ケイ素化合物を製造することができる。 With such a method for producing an organosilicon compound, it is possible to produce an organosilicon compound having both a norbornene structure and a hydrosilyl group in one molecule.
このとき、前記ノルボルネン構造を有する化合物を下記一般式（３）で表される末端アルケニル基含有ノルボルネン化合物とし、
前記ヒドロシリル基を有する化合物を下記一般式（４）で表されるメトキシシランとし、
The compound having a hydrosilyl group is designated as methoxysilane represented by the following general formula (4).
このような方法であれば、簡単かつ効率よく、上記一般式（１）で表される有機ケイ素化合物を製造することができる。 With such a method, the organosilicon compound represented by the above general formula (1) can be easily and efficiently produced.
本発明の有機ケイ素化合物は、１分子中にノルボルネン構造とヒドロシリル基を有することで、ヒドロシリル化反応可能な不飽和基を有する他分子とヒドロシリル化反応し、かつノルボルネン由来の内部不飽和基を残すことができる有機ケイ素化合物である。そのため、白金触媒存在下、他分子中の各種のヒドロシリル化反応可能な不飽和基と反応させることができ、かつヒドロシリル化に関与しないノルボルネン構造中の内部不飽和基を残すことができる。該内部不飽和は過酸化物架橋やラジカル架橋等で架橋点として利用でき、架橋剤等として有用である。また、本発明の有機ケイ素化合物の製造方法は、上記の様な１分子中にノルボルネン構造とヒドロシリル基の両方を有する有機ケイ素化合物を製造することができる。 The organic silicon compound of the present invention has a norbornene structure and a hydrosilylation group in one molecule, so that it undergoes a hydrosilylation reaction with another molecule having an unsaturated group capable of hydrosilylation reaction, and leaves an internal unsaturated group derived from norbornene. It is an organic silicon compound that can be. Therefore, in the presence of a platinum catalyst, it is possible to react with various hydrosilylation-reactive unsaturated groups in other molecules, and it is possible to leave internal unsaturated groups in the norbornene structure that are not involved in hydrosilylation. The internal unsaturated can be used as a cross-linking point in peroxide cross-linking, radical cross-linking, etc., and is useful as a cross-linking agent or the like. Further, the method for producing an organosilicon compound of the present invention can produce an organosilicon compound having both a norbornene structure and a hydrosilyl group in one molecule as described above.
以下、本発明を詳細に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.
上述のように、１分子中にノルボルネン構造とヒドロシリル基の両方を有する有機ケイ素化合物が求められていた。 As described above, an organosilicon compound having both a norbornene structure and a hydrosilyl group in one molecule has been sought.
本発明者は、上記課題について鋭意検討を重ねた結果、１分子中にノルボルネン構造とヒドロシリル基を有する有機ケイ素化合物は、ヒドロシリル化反応可能な不飽和基を有する他分子と反応し、かつヒドロシリル化後の生成物がノルボルネン由来の不飽和基を残すことができるため、架橋剤として有用であることを見出し、本発明を完成した。 As a result of diligent studies on the above-mentioned problems, the present inventor reacts an organic silicon compound having a norbornene structure and a hydrosilyl group in one molecule with another molecule having an unsaturated group capable of hydrosilylation reaction, and hydrosilylates. The latter product was found to be useful as a cross-linking agent because it can leave unsaturated groups derived from norbornen, and the present invention was completed.
即ち、本発明は１分子中にノルボルネン構造とヒドロシリル基を有する有機ケイ素化合物であって、
下記一般式（１）で表されるノルボルネン構造含有オルガノハイドロジェンポリシロキサンである有機ケイ素化合物である。
It is an organosilicon compound which is a norbornene structure-containing organohydrogenpolysiloxane represented by the following general formula (1).
上記一般式（１）において、Ｒ１は、互いに独立に、炭素数１〜１０のアルキル基または炭素数６〜１０のアリール基を表す。Ｒ１において、炭素数１〜１０のアルキル基としては、直鎖状、環状、分枝状のいずれでもよく、その具体例としては、メチル、エチル、ｎ−プロピル、ｉ−プロピル、ｎ−ブチル、イソブチル、ｓ−ブチル、ｔ−ブチル、ｎ−ペンチル、ネオペンチル、ｎ−ヘキシル、ｎ−ヘプチル、ｎ−オクチル、ｎ−ノニル、ｎ−デシル、シクロプロピル、シクロブチル、シクロペンチル、シクロヘキシル、シクロヘプチル、シクロオクチル基等が挙げられる。
また、炭素数６〜１０のアリール基の具体例としては、フェニル、α−ナフチル、β−ナフチル基等が挙げられる。
これらの中でも、Ｒ１としては、直鎖のアルキル基が好ましく、メチル基、エチル基がより好ましい。
In the above general formula (1), R 1 represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms independently of each other. In R 1, the alkyl group having 1 to 10 carbon atoms, straight-chain, cyclic, may be either branched, and specific examples thereof include methyl, ethyl, n- propyl, i- propyl, n- butyl , Isobutyl, s-butyl, t-butyl, n-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclo Examples include octyl groups.
Specific examples of the aryl group having 6 to 10 carbon atoms include phenyl, α-naphthyl, β-naphthyl group and the like.
Among these, R 1, preferably a straight chain alkyl group, a methyl group, an ethyl group are more preferable.
また、Ｒ２は互いに独立に、水素原子または炭素数１〜１０のアルキル基を示す。炭素数１〜１０のアルキル基としては、上記の通りであるが、好ましくは水素原子である。 Further, R 2 independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. The alkyl group having 1 to 10 carbon atoms is as described above, but is preferably a hydrogen atom.
また、一般式（１）において、ｌは２〜１０であり、好ましくは２〜５、更に好ましくは２である。ｍは１〜３の整数であり、好ましくは２である。ｎは０〜１０の整数であり、好ましくは０〜５、更に好ましくは０〜３である。 Further, in the general formula (1), l is 2 to 10, preferably 2 to 5, and more preferably 2. m is an integer of 1 to 3, preferably 2. n is an integer of 0 to 10, preferably 0 to 5, and more preferably 0 to 3.
一般式（１）で表されるノルボルネン構造含有オルガノハイドロジェンポリシロキサンの好ましい例としては、上記Ｒ１のうち、末端のケイ素原子に結合するＲ１がメチル基であり、Ｒ２が水素原子である、下記式（６−１）〜（６−５）等で表されるものを挙げられるが、これらに限定されるものではない。 Preferred examples of the norbornene structure-containing organohydrogenpolysiloxane represented by general formula (1), of the above R 1, R 1 bonded to the silicon atom of the terminal is a methyl group, R 2 is a hydrogen atom Some of the following formulas (6-1) to (6-5) and the like can be mentioned, but the present invention is not limited thereto.
以上のように、本発明の有機ケイ素化合物は、１分子中にノルボルネン構造とヒドロシリル基の両方を有する有機ケイ素化合物である。本発明の有機ケイ素化合物は、１分子中にノルボルネン構造とヒドロシリル基の両方を有するため、白金触媒存在下、他分子中の各種のヒドロシリル化反応可能な不飽和基と反応させることができ、かつヒドロシリル化に関与しない内部不飽和基をノルボルネン構造中に残すことができる。該内部不飽和は、例えば、過酸化物架橋やラジカル架橋等で架橋点として利用できるため、架橋剤等として有用である。 As described above, the organosilicon compound of the present invention is an organosilicon compound having both a norbornene structure and a hydrosilyl group in one molecule. Since the organic silicon compound of the present invention has both a norbornene structure and a hydrosilylation group in one molecule, it can react with various hydrosilylation-reactive unsaturated groups in other molecules in the presence of a platinum catalyst, and Internal unsaturated groups that are not involved in hydrosilylation can remain in the norbornen structure. The internal unsaturated can be used as a cross-linking point in, for example, peroxide cross-linking or radical cross-linking, and is therefore useful as a cross-linking agent or the like.
また、本発明の有機ケイ素化合物の製造方法は、１分子中にノルボルネン構造とヒドロシリル基を有する有機ケイ素化合物の製造方法であって、
ノルボルネン構造を有する化合物とヒドロシリル基を有する化合物をヒドロシリル化反応させることで、ノルボルネン構造含有中間体を合成し、
該ノルボルネン構造含有中間体を下記一般式（２）で表されるハイドロジェンシロキサンと酸平衡させることで、下記一般式（１）で表されるノルボルネン構造含有オルガノハイドロジェンポリシロキサンを製造する有機ケイ素化合物の製造方法である。
By hydrosilylating a compound having a norbornene structure and a compound having a hydrosilyl group, a norbornene structure-containing intermediate is synthesized.
Organosilicon for producing a norbornene structure-containing organohydrogenpolysiloxane represented by the following general formula (1) by acid equilibrating the norbornene structure-containing intermediate with a hydrogen siloxane represented by the following general formula (2). It is a method for producing a compound.
このとき、ノルボルネン構造を有する化合物を下記一般式（３）で表される末端アルケニル基含有ノルボルネン化合物とし、
ヒドロシリル基を有する化合物を下記一般式（４）で表されるメトキシシランとし、
The compound having a hydrosilyl group is methoxysilane represented by the following general formula (4).
このようにすれば、簡単かつ効率よく、上記一般式（１）で表される有機ケイ素化合物を製造することができる。 By doing so, the organosilicon compound represented by the above general formula (1) can be easily and efficiently produced.
本発明の有機ケイ素化合物の製造方法は、例えば、上記一般式（４）で表されるメトキシシランと、上記一般式（３）で表される末端アルケニル基含有ノルボルネン化合物１モル当量以上を、ヒドロシリル化触媒存在下で付加反応（ヒドロシリル化反応）させ、上記一般式式（５）で表されるノルボルネン含有アルコキシシラン（ノルボルネン構造含有中間体）を得る。 In the method for producing an organosilicon compound of the present invention, for example, methoxysilane represented by the above general formula (4) and 1 mol or more of a terminal alkenyl group-containing norbornen compound represented by the above general formula (3) are hydrosilylated. An addition reaction (hydrosilylation reaction) is carried out in the presence of a chemical catalyst to obtain a norbornene-containing alkoxysilane (norbornene structure-containing intermediate) represented by the above general formula (5).
上記付加反応は無溶剤でも、溶媒の存在下で行ってもよい。溶媒は従来公知のものであればよく、特に制限されるものでない。反応温度は特に制限されるものでないが、使用する溶媒の沸点を超えない程度の温度が好ましい。例えば、０℃〜１２０℃の温度で行われるのがよい。 The addition reaction may be carried out without a solvent or in the presence of a solvent. The solvent may be any conventionally known solvent and is not particularly limited. The reaction temperature is not particularly limited, but is preferably a temperature that does not exceed the boiling point of the solvent used. For example, it is preferable to carry out at a temperature of 0 ° C to 120 ° C.
その後、上記一般式（２）で示されるハイドロジェンシロキサンと酸平衡させることで、上記一般式（１）で示される有機ケイ素化合物が得られる。 Then, by acid equilibrating with the hydrogen siloxane represented by the general formula (2), the organosilicon compound represented by the general formula (1) can be obtained.
このような有機ケイ素化合物の製造方法であれば、１分子中にノルボルネン構造とヒドロシリル基の両方を有する有機ケイ素化合物を製造することができる。 With such a method for producing an organosilicon compound, it is possible to produce an organosilicon compound having both a norbornene structure and a hydrosilyl group in one molecule.
以下、実施例を挙げて本発明について詳細に説明するが、これは本発明を限定するものではない。なお、化合物の構造は、１Ｈ−ＮＭＲより決定し、また、ガスクロマトグラフィーによる分析は下記の条件で行った。 Hereinafter, the present invention will be described in detail with reference to examples, but this is not limited to the present invention. The structure of the compound was determined by 1 H-NMR, and the analysis by gas chromatography was performed under the following conditions.
［ガスクロマトグラフィー（ＧＣ）分析］
ＧＣ装置：アジレント・テクノロジー（株）製 ＨＰ７８９０Ｂ、
検出器：熱伝導度型検出器（ＴＣＤ）、
カラム：ＤＢ−５ （長さ３０ｍ×内径０．５３０ｍｍ×膜厚１．５０μｍ）、
カラム温度：１００℃→昇温１５℃／分→３００℃（１０分保持）、
測定時間：計２３．３分、
注入口温度：２５０℃、
検出器温度：３００℃、
キャリアガス：Ｈｅ、
キャリアガス流量：３．０ｍＬ／ｍｉｎ。
[Gas Chromatography (GC) Analysis]
GC equipment: HP789B, manufactured by Agilent Technologies, Inc.
Detector: Thermal conductivity type detector (TCD),
Column: DB-5 (length 30 m x inner diameter 0.530 mm x film thickness 1.50 μm),
Column temperature: 100 ° C → temperature rise 15 ° C / min → 300 ° C (hold for 10 minutes),
Measurement time: 23.3 minutes in total,
Injection port temperature: 250 ° C,
Detector temperature: 300 ° C,
Carrier gas: He,
Carrier gas flow rate: 3.0 mL / min.
（実施例１）
撹拌機、還流冷却器、滴下ロートおよび温度計を備えた３００ｍｌセパラブルフラスコに、５−ビニル−２−ノルボルネン ７２．１ｇ（０．６モル）と、１，３−ジビニル−１，１，３，３−テトラメチルジシロキサン白金錯体のジメチルシロキサン溶液（Ｐｔ濃度１質量％） ０．９４ｇを添加し、メチルジメトキキシラン ９５．４ｇ（０．９０モル）を内温３０〜４０℃で１時間かけて滴下した。
(Example 1)
In a 300 ml separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 72.1 g (0.6 mol) of 5-vinyl-2-norbornene and 1,3-divinyl-1,1,3 , 3-Tetramethyldisiloxane Platinum complex dimethylsiloxane solution (Pt concentration 1% by mass) 0.94 g was added, and 95.4 g (0.90 mol) of methyldimethoxylan was added at an internal temperature of 30 to 40 ° C. for 1 hour. Dropped over.
その後、５０℃で４時間撹拌し、ガスクロマトグラフィーで分析した結果、５−ビニル−２−ノルボルネンのピークが消滅していた。得られた溶液を１６ｍｍＨｇ、１３０℃の条件下で蒸留精製し、無色透明液体６９ｇを得た。該液体を１Ｈ−ＮＭＲにより測定したところ、下記式（７）で表されるノルボルネン構造含有アルコキシシランであることを確認した。 Then, the mixture was stirred at 50 ° C. for 4 hours and analyzed by gas chromatography. As a result, the peak of 5-vinyl-2-norbornene disappeared. The obtained solution was distilled and purified under the conditions of 16 mmHg and 130 ° C. to obtain 69 g of a colorless transparent liquid. When the liquid was measured by 1 H-NMR, it was confirmed that it was a norbornene structure-containing alkoxysilane represented by the following formula (7).
撹拌機、還流冷却器、滴下ロートおよび温度計を備えた５０ｍｌセパラブルフラスコに塩酸 ０．３７ｇ（０．０１モル）と水 １．５ｇ（０．０８３モル）及び両末端にヒドロシリル基を有する１，１，３，３−テトラメチルジシロキサン １２．１ｇ（０．０９モル）を納め、上記式（７）のノルボルネン含有アルコキシシラン １１．３ｇ（０．０５モル）を内温５〜１０℃で１時間かけて滴下した。 0.37 g (0.01 mol) of hydrochloric acid and 1.5 g (0.083 mol) of water in a 50 ml separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, and having hydrosilyl groups at both ends 1 , 1,3,3-Tetramethyldisiloxane 12.1 g (0.09 mol) and 11.3 g (0.05 mol) of the norbornene-containing alkoxysilane of the above formula (7) at an internal temperature of 5 to 10 ° C. It was dropped over 1 hour.
その後１５℃で４時間撹拌し、１０％硫酸ナトリウム水溶液で３回水洗した後、１６ｍｍＨｇ、５０℃の条件下で蒸留精製したところ１１ｇの主留が得られ、該主留の構造を１Ｈ−ＮＭＲより、下記式（６−１）のノルボルネン構造含有シロキサンと確認した。 Then, the mixture was stirred at 15 ° C. for 4 hours, washed with 10% sodium sulfate aqueous solution three times, and then distilled and purified under the conditions of 16 mmHg and 50 ° C. to obtain 11 g of main distillate, and the structure of the main distillate was 1 H-. From NMR, it was confirmed that the siloxane contained the norbornene structure of the following formula (6-1).
以上のとおり、本発明の実施例によれば、１分子中にノルボルネン構造とヒドロシリル基の両方を有する有機ケイ素化合物を得ることができた。 As described above, according to the examples of the present invention, it was possible to obtain an organosilicon compound having both a norbornene structure and a hydrosilyl group in one molecule.
なお、本発明は、上記実施形態に限定されるものではない。上記実施形態は例示であり、本発明の特許請求の範囲に記載された技術的思想と実質的に同一な構成を有し、同様な作用効果を奏するものは、いかなるものであっても本発明の技術的範囲に包含される。 The present invention is not limited to the above embodiment. The above-described embodiment is an example, and any of the above-described embodiments having substantially the same configuration as the technical idea described in the claims of the present invention and having the same effect and effect is the present invention. Is included in the technical scope of.
Claims (3)
下記一般式（１）で表されるノルボルネン構造含有オルガノハイドロジェンポリシロキサンである有機ケイ素化合物。
An organosilicon compound which is a norbornene structure-containing organohydrogenpolysiloxane represented by the following general formula (1).
ノルボルネン構造を有する化合物とヒドロシリル基を有する化合物をヒドロシリル化反応させることで、ノルボルネン構造含有中間体を合成し、
該ノルボルネン構造含有中間体を下記一般式（２）で表されるハイドロジェンシロキサンと酸平衡させることで、下記一般式（１）で表されるノルボルネン構造含有オルガノハイドロジェンポリシロキサンを製造することを特徴とする有機ケイ素化合物の製造方法。
By hydrosilylating a compound having a norbornene structure and a compound having a hydrosilyl group, a norbornene structure-containing intermediate is synthesized.
By acid equilibrating the norbornene structure-containing intermediate with a hydrogen siloxane represented by the following general formula (2), a norbornene structure-containing organohydrogenpolysiloxane represented by the following general formula (1) can be produced. A method for producing an organosilicon compound.
前記ヒドロシリル基を有する化合物を下記一般式（４）で表されるメトキシシランとし、
The compound having a hydrosilyl group is designated as methoxysilane represented by the following general formula (4).
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