JP5178098B2 - Alicyclic vinyl ether compounds - Google Patents
Alicyclic vinyl ether compounds Download PDFInfo
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- JP5178098B2 JP5178098B2 JP2007228114A JP2007228114A JP5178098B2 JP 5178098 B2 JP5178098 B2 JP 5178098B2 JP 2007228114 A JP2007228114 A JP 2007228114A JP 2007228114 A JP2007228114 A JP 2007228114A JP 5178098 B2 JP5178098 B2 JP 5178098B2
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本発明は、新規脂環式ビニルエーテル化合物に関し、更に詳しくは、各種樹脂の改質剤や光学材料、電気・電子材料などに用いられる低誘電率樹脂の原料として有用な脂環式ビニルエーテル化合物に関する。 The present invention relates to a novel alicyclic vinyl ether compound, and more particularly to an alicyclic vinyl ether compound useful as a raw material for low dielectric constant resins used in various resin modifiers, optical materials, electrical / electronic materials, and the like.
従来、光学材料や電気・電子材料等の重合体組成物としてアクリル系化合物が広く用いられてきたが、アクリル系化合物は皮膚刺激性や臭気を有するため、その取り扱い性に問題があり、更に、前記重合体組成物の利用分野の広がりとともに、樹脂への要求性能が高度化しており、作業性や吸湿性に問題を有するアクリル系化合物は最近のニーズには必ずしも十分対応できなくなってきている。一方、ビニルエーテル化合物の製造については種々の文献が知られているが（例えば特許文献１参照）、上記ニーズに応えられるようなものは知られていない。 Conventionally, acrylic compounds have been widely used as polymer compositions such as optical materials and electrical / electronic materials, but acrylic compounds have skin irritation and odor, and thus have problems in handling, Along with the expansion of the field of application of the polymer composition, the required performance of the resin has become higher, and acrylic compounds having problems in workability and hygroscopicity have not always been able to sufficiently meet recent needs. On the other hand, although various literatures are known about manufacture of a vinyl ether compound (for example, refer to patent documents 1), what can respond to the above-mentioned needs is not known.
従って、本発明の目的は、前述の従来技術の問題点を解消し、光学材料や電気・電子材料の分野における高度な要求性能に応えることができ、更には、従来のアクリル系化合物の吸湿性の問題点を改良した、低誘電率樹脂の原料として有用な脂環式ビニルエーテルを提供することにある。 Therefore, the object of the present invention is to solve the above-mentioned problems of the prior art, meet the high required performance in the field of optical materials and electrical / electronic materials, and further absorb the hygroscopicity of conventional acrylic compounds. An object of the present invention is to provide an alicyclic vinyl ether which is useful as a raw material for a low dielectric constant resin.
すなわち、本発明に従えば、式（Ｉ）：
で表される脂環式ビニルエーテルが提供される。
That is, according to the present invention, the formula (I):
The alicyclic vinyl ether represented by these is provided.
本発明に係る式（Ｉ）の脂環式ビニルエーテルは、嵩高い置換基の存在により低誘電率で、誘電損失が低く、耐熱性に優れ、また、大きな脂環骨格により、吸湿性が低く、更に、ビニルエーテル基による金属等への密着性が高い、低誘電率樹脂原料として期待できる。 The alicyclic vinyl ether of the formula (I) according to the present invention has a low dielectric constant, low dielectric loss, excellent heat resistance due to the presence of a bulky substituent, and low hygroscopicity due to a large alicyclic skeleton, Furthermore, it can be expected as a low dielectric constant resin material having high adhesion to a metal or the like due to a vinyl ether group.
本発明者らは、上記目的を達成すべく鋭意検討した結果、従来のそれよりも嵩高い置換基により低誘電率で、誘電損失が低く、耐熱性に優れ、また、大きな脂環骨格により吸湿性が低く、更に、ビニルエーテル基による金属等への密着性が期待できる低誘電率樹脂の原料として有用な脂環式ビニルエーテル化合物を見出し本発明を完成させた。 As a result of intensive studies to achieve the above object, the present inventors have found that the substituent is bulkier than the conventional one, has a low dielectric constant, low dielectric loss, excellent heat resistance, and has a large alicyclic skeleton to absorb moisture. The present invention was completed by finding an alicyclic vinyl ether compound that is useful as a raw material for a low dielectric constant resin that is low in properties and that can be expected to have adhesion to a metal or the like due to a vinyl ether group.
以下、本発明に係る脂環式ビニルエーテルについて更に詳しく説明する。
本発明に係る脂環式ビニルエーテルは、具体的には、式（II）で表わされるヘプタシクロテトラデカン骨格を有するビニルエーテルである。
Hereinafter, the alicyclic vinyl ether according to the present invention will be described in more detail.
The alicyclic vinyl ether according to the present invention is specifically a vinyl ether having a heptacyclotetradecane skeleton represented by the formula (II).
式（II）で表される化合物において、Ｒ1はビニロキシ基又は水素を示し、Ｒ2はビニロキシ基又は水素を示し、Ｒ1及びＲ2の少なくとも一方はビニロキシ基を示す。即ち、本発明のビニルエーテルは、分子中に少なくとも１つのビニロキシ基を有する化合物である。 In the compound represented by the formula (II), R 1 represents a vinyloxy group or hydrogen, R 2 represents a vinyloxy group or hydrogen, and at least one of R 1 and R 2 represents a vinyloxy group. That is, the vinyl ether of the present invention is a compound having at least one vinyloxy group in the molecule.
なお、本発明の脂環式ビニルエーテルは、例えばヘプタシクロテトラデカノールから誘導することができ、このヘプタシクロテトラデカノールが１−ヘプタシクロテトラデカノールと、７−ヘプタシクロテトラデカノールの混合物である場合には、得られる本発明のヘプタシクロテトラデカビニルエーテルも混合物となり、その混合比はアルコールの混合比（例えば１−体：７−体＝２．０：０．６〜１．０、好ましくは２：１）が反映される。 The alicyclic vinyl ether of the present invention can be derived from, for example, heptacyclotetradecanol, and this heptacyclotetradecanol is a mixture of 1-heptacyclotetradecanol and 7-heptacyclotetradecanol. In some cases, the resulting heptacyclotetradecavinyl ether of the present invention also becomes a mixture, and the mixing ratio thereof is a mixing ratio of alcohols (for example, 1-isomer: 7-isomer = 2.0: 0.6 to 1.0, preferably Reflects 2: 1).
ヘプタシクロテトラデカン骨格を有するビニルエーテルを製造する際の原料であるヘプタシクロテトラデカノールは公知の化合物であり、その合成方法は、例えばJ. Org. Chem. 1988, 53, 1102-に記載されている。 Heptacyclotetradecanol, which is a raw material for producing a vinyl ether having a heptacyclotetradecane skeleton, is a known compound, and its synthesis method is described in, for example, J. Org. Chem. 1988, 53 , 1102- .
上記の原料により本発明の脂環式ビニルエーテル、具体的にはヘプタシクロテトラデカビニルエーテルを製造する方法には特に制限は無く、公知の方法を使用することができる。即ち、ヘプタシクロテトラデカノールを水酸化カリウム、水酸化ナトリウムなどのアルカリ金属化合物の存在下に、ジメチルスルホキシド（ＤＭＳＯ）、ジメチルイミダゾリジノン（ＤＭＩ）などの溶媒を使用して、アセチレン雰囲気下で反応させる方法や、ビニル基交換反応（特開平５−２２１９０８号公報、特開２００３−７３３２１号公報及びJ. Org. Chem. 2003, 68, 5225-など参照）などによることができる。 There is no restriction | limiting in particular in the method of manufacturing the alicyclic vinyl ether of this invention by the said raw material, specifically heptacyclotetradeca vinyl ether, A well-known method can be used. That is, heptacyclotetradecanol is used in the presence of an alkali metal compound such as potassium hydroxide or sodium hydroxide in a acetylene atmosphere using a solvent such as dimethyl sulfoxide (DMSO) or dimethylimidazolidinone (DMI). It can be carried out by a reaction method or a vinyl group exchange reaction (see JP-A-5-221908, JP-A-2003-73321 and J. Org. Chem. 2003, 68 , 5225-).
本発明のヘプタシクロテトラデカビニルエーテルの好ましい製造方法を具体的に記載すれば、ヘプタシクロテトラデカノール又はその異性体混合物と酢酸ビニルを、ジ−μ−クロロビス（１，５−シクロオクタジエン）イリジウムなどのイリジウム触媒と炭酸ナトリウム等の塩基性化合物の存在下に、トルエンなどの有機溶媒中で窒素などの不活性気体雰囲気に反応させることによって所望の化合物を得ることができる。この反応温度や反応時間には特に制限はないが、例えば７０〜１００℃で２〜２４時間反応させるのが好ましい。使用するヘプタシクロテトラデカノールと酢酸ビニルの反応比には特に制限はないが、ヘプタシクロテトラデカノール１モルに対し酢酸ビニル１〜４モル程度反応させるのが好ましい。 If the preferable manufacturing method of the heptacyclotetradeca vinyl ether of this invention is described concretely, heptacyclotetradecanol or its isomer mixture and vinyl acetate will be di-micro-chlorobis (1, 5- cyclooctadiene) iridium. The desired compound can be obtained by reacting in an inert gas atmosphere such as nitrogen in an organic solvent such as toluene in the presence of an iridium catalyst such as sodium carbonate and a basic compound such as sodium carbonate. Although there is no restriction | limiting in particular in this reaction temperature and reaction time, For example, it is preferable to make it react at 70-100 degreeC for 2 to 24 hours. Although there is no restriction | limiting in particular in the reaction ratio of the heptacyclotetradecanol and vinyl acetate to be used, It is preferable to make it react about 1-4 mol of vinyl acetate with respect to 1 mol of heptacyclotetradecanol.
以下、実施例により本発明を詳細に説明するが、本発明をこれら実施例に限定するものでないことはいうまでもない。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, it cannot be overemphasized that this invention is not what is limited to these Examples.
実施例１
［Ｉｒ（ｃｏｄ）Ｃｌ］2（ジ−μ−クロロビス（１，５−シクロオクタジエン）ＩＩイリジウム）（２ｍｇ，０．００３ｍｍｏｌ）と炭酸ナトリウム（２１ｍｇ，０．２ｍｍｏｌ）をトルエン０．８ｍｌと混合し、ヘプタシクロテトラデカノール異性体混合物（６０ｍｇ，０．３ｍｍｏｌ）及び酢酸ビニル（８４ｍｇ，１．０ｍｍｏｌ）を加え、窒素雰囲気下、１００℃で２時間半攪拌することにより、ヘプタシクロテトラデカビニルエーテル混合物を収率４０％で得た。これをカラムクロマトにより分離し、１−ヘプタシクロテトラデカビニルエーテル及び７−ヘプタシクロテトラデカビニルエーテルを得た。
Example 1
[Ir (cod) Cl] 2 (di-μ-chlorobis (1,5-cyclooctadiene) II iridium) (2 mg, 0.003 mmol) and sodium carbonate (21 mg, 0.2 mmol) mixed with 0.8 ml of toluene Heptacyclotetradecanol isomer mixture (60 mg, 0.3 mmol) and vinyl acetate (84 mg, 1.0 mmol) were added, and the mixture was stirred at 100 ° C. for 2 hours and a half in a nitrogen atmosphere, to give heptacyclotetradecanavinyl ether. The mixture was obtained in 40% yield. This was separated by column chromatography to obtain 1-heptacyclotetradecavinyl ether and 7-heptacyclotetradecavinyl ether.
生成物の構造は1Ｈ ＮＭＲスペクトルにより以下の通り確認した。
１−ヘプタシクロテトラデカビニルエーテル（図１参照）
1Ｈ ＮＭＲスペクトルデータ（測定条件：ブルカ−バイオスピン株式会社製 ４００ＭＨｚ 核磁気共鳴装置を使用、測定溶媒：ＣＤＣｌ3）ではビニル基に基づくピークが６．３，４．４，４．０ｐｐｍに、脂環骨格に基づくピークが２．６〜１．７ｐｐｍに観測されたことから１−ヘプタシクロテトラデカビニルエーテルが生成していることが確認された。
The structure of the product was confirmed by 1 H NMR spectrum as follows.
1-heptacyclotetradecavinyl ether (see FIG. 1)
In 1 H NMR spectrum data (measurement condition: 400 MHz nuclear magnetic resonance apparatus manufactured by Bruker BioSpin Corporation, measurement solvent: CDCl 3 ), the peak based on the vinyl group is 6.3, 4.4, and 4.0 ppm. Since a peak based on the alicyclic skeleton was observed at 2.6 to 1.7 ppm, it was confirmed that 1-heptacyclotetradecavinyl ether was generated.
７−ヘプタシクロテトラデカビニルエーテル（図２参照）
1Ｈ ＮＭＲスペクトルデータ（測定条件：ブルカ−バイオスピン株式会社製 ４００ＭＨｚ 核磁気共鳴装置を使用、測定溶媒：ＣＤＣｌ3）ではビニル基に基づくピークが６．３，４．２，３．９ｐｐｍに、脂環骨格に基づくピークが２．６〜１．５ｐｐｍに観測されたことから７−ヘプタシクロテトラデカビニルエーテルが生成していることが確認された。
7-heptacyclotetradecavinyl ether (see FIG. 2)
In 1 H NMR spectrum data (measurement conditions: 400 MHz nuclear magnetic resonance apparatus manufactured by Bruker BioSpin Corporation, measurement solvent: CDCl 3 ), the peak based on the vinyl group is 6.3, 4.2, and 3.9 ppm. Since a peak based on the alicyclic skeleton was observed at 2.6 to 1.5 ppm, it was confirmed that 7-heptacyclotetradecavinyl ether was generated.
本発明のヘプタシクロテトラデカビニルエーテルは、嵩高い置換基により低誘導率で、誘電損失が低く、耐熱性に優れ、また、大きな脂環骨格により吸湿性が低く、更に、ビニルエーテル基による金属等への密着性が期待できるので低誘電率樹脂の原料として、更に、光学材料、電気・電子材料の分野における高度な要求性能に対応し、更には、従来のアクリル系化合物による吸湿性の問題を改善するものとして期待できる。 The heptacyclotetradecavinyl ether of the present invention has a low induction rate due to bulky substituents, low dielectric loss, excellent heat resistance, low hygroscopicity due to a large alicyclic skeleton, and further to metals such as vinyl ether groups. As a raw material for low dielectric constant resins, it can also meet the high performance requirements in the fields of optical materials and electrical / electronic materials, and further improve the hygroscopic problems caused by conventional acrylic compounds. Can be expected.
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