JP2007217515A - New aromatic ether compound and photopolymerization initiator - Google Patents
New aromatic ether compound and photopolymerization initiator Download PDFInfo
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Abstract
Description
本発明は新規な芳香族エーテル化合物及びその製造方法と光重合開始剤に関する。 The present invention relates to a novel aromatic ether compound, a method for producing the same, and a photopolymerization initiator.
エポキシ化合物に代表される環状エーテル化合物やビニル化合物等の重合反応において用いられる光カチオン重合開始剤はエレクトロニクス、光通信の分野において非常に重要である。しかし、従来の開始剤はハロゲン、窒素、ホウ素、硫黄、リン、および金属を少なくとも一種含んでおり（特許文献１〜４など）、特殊な除去プロセスを行わない限り重合体中にこれらが残存し、わずかな量であっても素子の品質悪化の原因となっていた。また、焼却するとそれぞれ有害なハロゲン化合物、NOx、SOxが排出される可能性が高く、環境への負荷が大きかった。
最近になって基本骨格に、窒素、ホウ素、硫黄、リン、および金属を含まないエーテル化合物よりなる光開始剤が報告されている（例えば、非特許文献１参照。）。しかし、この光重合開始剤は、ナフチル基上にシアノ基を有し、これによる生成重合体の汚染、品質悪化は避けられず、また、これを用いた光カチオン重合反応による重合体の収率は不十分であった。
Recently, a photoinitiator composed of an ether compound containing no nitrogen, boron, sulfur, phosphorus, or metal in the basic skeleton has been reported (for example, see Non-Patent Document 1). However, this photopolymerization initiator has a cyano group on the naphthyl group, so that contamination of the produced polymer and deterioration of the quality are inevitable, and the yield of the polymer due to the photocationic polymerization reaction using this polymer Was insufficient.
本発明の課題はハロゲン、窒素、ホウ素、硫黄、リン、および金属を全く含まない、光カチオン重合において高い効率で機能する光重合開始剤と、この用途に好適な新規な芳香族エーテル化合物及びその製造方法を提供することにある。 An object of the present invention is to provide a photopolymerization initiator that does not contain halogen, nitrogen, boron, sulfur, phosphorus, and metal at all and functions with high efficiency in photocationic polymerization, a novel aromatic ether compound suitable for this use, and its It is to provide a manufacturing method.
本発明者らは上記目的を達成すべく鋭意研究を行った結果、新規な芳香族エーテル化合物を見出し、本発明を完成させるに至った。即ち、本発明は、
（１） 下記一般式（Ｉ）で表される芳香族エーテル化合物、
一般式（Ｉ）
As a result of intensive studies to achieve the above object, the present inventors have found a novel aromatic ether compound and have completed the present invention. That is, the present invention
(1) an aromatic ether compound represented by the following general formula (I):
Formula (I)
（式中、Ar1は置換されていてもよく、かつ2つ以上のベンゼン環が縮環した芳香族炭化水素基を示す。Ar2は置換されていてもよく、かつ３つ以上のベンゼン環が縮環した芳香族炭化水素基を示す。R1およびR2は水素原子または置換されていてもよい炭化水素基を示す。）、
（２） 前記（１）に記載の一般式（Ｉ）で表される芳香族エーテル化合物よりなる光重合開始剤、及び
（３） Ar2OHとAr1C(R1R2)Xとを反応させることを特徴とする（１）に記載の一般式（Ｉ）で表される芳香族エーテル化合物の製造方法（式中Ar1、Ar2、R1及びR2は前記と同じ意味を持つ。Ｘはハロゲン原子、水酸基又は−ＳＯ3Ｑで表される基（ここで、Ｑは置換されていてもよい１価の炭化水素基を示す。）を示す。）
を提供するものである。
(In the formula, Ar 1 may be substituted and represents an aromatic hydrocarbon group having two or more benzene rings condensed. Ar 2 may be substituted and three or more benzene rings. Represents a condensed aromatic hydrocarbon group, R 1 and R 2 represent a hydrogen atom or an optionally substituted hydrocarbon group).
(2) A photopolymerization initiator comprising the aromatic ether compound represented by the general formula (I) described in (1), and (3) Ar 2 OH and Ar 1 C (R 1 R 2 ) X A process for producing an aromatic ether compound represented by the general formula (I) according to (1), wherein Ar 1 , Ar 2 , R 1 and R 2 have the same meaning as described above X represents a halogen atom, a hydroxyl group or a group represented by —SO 3 Q (wherein Q represents a monovalent hydrocarbon group which may be substituted).
Is to provide.
本発明の芳香族エーテル化合物はその骨格構成元素として窒素、ホウ素、硫黄、リン、金属元素などのヘテロ原子を含有しない新規な化合物である。この芳香族エーテル化合物の存在下で高効率で光カチオン重合が進行し、得られる高分子はこれを樹脂材料とする電気ないしは光素子のような部品の品質悪化の原因となるハロゲン、シアノ基、窒素、ホウ素、硫黄、リン、金属などを含まない。また、この樹脂部品を焼却しても有害なハロゲン化合物、NOx、SOxが排出されることはなく、環境への負荷を著しく低減することを可能にする。
本発明によれば上記のような優れた性質を有する芳香族エーテル化合物を好収率で製造できる。
The aromatic ether compound of the present invention is a novel compound that does not contain heteroatoms such as nitrogen, boron, sulfur, phosphorus, and metal elements as skeleton constituent elements. Photocationic polymerization proceeds with high efficiency in the presence of this aromatic ether compound, and the resulting polymer is a halogen, a cyano group, which causes deterioration of the quality of parts such as electricity or optical elements using this as a resin material, Does not contain nitrogen, boron, sulfur, phosphorus, metal, etc. In addition, even if this resin component is incinerated, no harmful halogen compounds, NOx, and SOx are emitted, and the environmental load can be significantly reduced.
According to the present invention, an aromatic ether compound having excellent properties as described above can be produced in good yield.
以下、本発明を詳細に説明する。
上記一般式（Ｉ）において、好ましくは、Ar1は置換されていてもよく、かつ2以上10以下のベンゼン環が縮環した芳香族炭化水素基を表す。Ar2は置換されていてもよい３以上10以下のベンゼン環が縮環した芳香族炭化水素基を表す。ただし、十分な溶解性を保つためにAr1は、好ましくは５以下、さらに好ましくは2つのベンゼン環が縮環した芳香族炭化水素基であり、Ar2は好ましくは５以下、さらに好ましくは３つのベンゼン環が縮環した芳香族炭化水素基である。R1およびR2は水素原子または炭化水素基を表す。
Hereinafter, the present invention will be described in detail.
In the general formula (I), Ar 1 preferably represents an aromatic hydrocarbon group which may be substituted and has 2 or more and 10 or less benzene rings condensed. Ar 2 represents an aromatic hydrocarbon group in which 3 or more and 10 or less benzene rings which may be substituted are condensed. However, Ar 1 is preferably an aromatic hydrocarbon group in which two benzene rings are condensed in order to maintain sufficient solubility, and Ar 2 is preferably 5 or less, more preferably 3 An aromatic hydrocarbon group in which two benzene rings are condensed. R 1 and R 2 represent a hydrogen atom or a hydrocarbon group.
Ar2におけるベンゼン環が縮環した芳香族炭化水素基として、下記の例示される芳香環上の少なくとも１つの炭素原子上から、水素原子を１つ取り除くことにより示される基であり、これらは、上記のように置換されていてもよい。 An aromatic hydrocarbon group having a condensed benzene ring in Ar 2 is a group represented by removing one hydrogen atom from at least one carbon atom on the aromatic ring exemplified below, and these are: It may be substituted as described above.
Ar1におけるベンゼン環が縮環した芳香族炭化水素基は上記の他にナフタレンの炭素原子１つから、水素原子を１つ取り除くことにより示される基も含まれ、置換されていてもよい。
Ar1の置換されていてもよいベンゼン環が縮環した芳香族炭化水素基については、好ましくはナフタレンの１、２、３、４、５、６、７、８位の炭素原子の１つの上の、水素原子を１つ取り除くことにより示される基であり、より好ましくはナフタレンの１、２、４、５位の炭素原子の１つの上の水素原子を１つ結合する取り除くことにより示される基であり、さらに好ましくは、ナフタレンの炭素原子１つから水素原子を１つ取り除くことにより示される基である。Ar2の置換されていてもよいベンゼン環が縮環した芳香族炭化水素基については、好ましくは１、２、３、４、５、６、７、８位の炭素原子１つから水素原子を１つ取り除くことにより示される基であり、より好ましくは１、２、４、５位の炭素原子１つから結合する水素原子を１つ取り除くことにより示される基であり、さらに好ましくは、1の炭素原子１つから結合水素原子を１つ取り除くことにより示される基である。
In addition to the above, the aromatic hydrocarbon group having a condensed benzene ring in Ar 1 includes a group represented by removing one hydrogen atom from one carbon atom of naphthalene, and may be substituted.
For the aromatic hydrocarbon group in which the optionally substituted benzene ring of Ar 1 is condensed, preferably on one of the 1, 2, 3, 4, 5, 6, 7, 8 position carbon atoms of naphthalene. A group shown by removing one hydrogen atom, more preferably a group shown by removing one hydrogen atom on one of the 1, 2, 4, 5 position carbon atoms of naphthalene. And more preferably a group represented by removing one hydrogen atom from one carbon atom of naphthalene. For the aromatic hydrocarbon group in which the optionally substituted benzene ring of Ar 2 is condensed, a hydrogen atom is preferably formed from one carbon atom at positions 1, 2, 3, 4, 5, 6, 7, and 8. A group represented by removing one, more preferably a group represented by removing one hydrogen atom bonded to one carbon atom at positions 1, 2, 4, and 5; It is a group represented by removing one bonded hydrogen atom from one carbon atom.
Ar1およびAr2のベンゼン環が縮環した芳香族炭化水素基の置換基としては、炭素原子、水素原子及び酸素原子からなる基が好ましく、好ましくは炭素原子数１〜２０の、より好ましくは１〜１２のアルコキシ基、好ましくは、炭素原子数７〜１９の、より好ましくは７〜１１のアラルキロキシ基、好ましくは炭素原子数６〜１８の、より好ましくは６〜１０のアリーロキシ基、水酸基、好ましくは炭素原子数１〜２０の、より好ましくは１〜１２のアルキル基、好ましくは炭素原子数６〜１８の、より好ましくは６〜１０のアリール基、好ましくは炭素原子数７〜１９の、より好ましくは７〜１１のアラルキル基、好ましくは炭素原子数２〜２１の、より好ましくは２〜１３のアルキロキシカルボニル基、好ましくは炭素原子数２〜２１の、より好ましくは２〜１３のアルキルカルボニロキシ基、好ましくは炭素原子数２〜２１の、より好ましくは２〜１３のアルキルカルボニル基又はアルデヒド基等が挙げられる。
アルコキシ基、アラルキロキシ基、アリーロキシ基の具体例としては、メトキシ基、エトキシ基、ｎ−プロピロキシ基、ｉｓｏ−プロピロキシ基、シクロプロピロキシ基、ｎ−ブチロキシ基、ｉｓｏ−ブチロキシ基、ｔ−ブチロキシ基、シクロブチロキシ基、ペンチロキシ基、ｉｓｏ−ペンチロキシ基、ｎｅｏ−ペンチロキシ基、シクロペンチロキシ基、ヘキシロキシ基、シクロヘキシロキシ基、メチルシクロヘキシロキシ基、シクロヘキセニロキシ基、シクロヘキサジエニロキシ基、メンチロキシ基、ピナニロキシ基、ビシクロヘプチロキシ（ノルボニロキシ）基、オクチロキシ基、ノニロキシ基、デシロキシ基、ウンデシロキシ基、ドデシロキシ基、１-フェニルエトキシ基、２-フェニルエチロキシ基、２−メチルフェニロキシ基、３−メチルフェニロキシ基、４−メチルフェニロキシ基、ベンジロキシ基、フェニロキシ基、キシリロキシ基、メシチロキシ基、クミロキシ基、１−ナフチロキシ基、２−ナフチロキシ基等が挙げられる。アルキル基の例としてはメチル基、エチル基、ｎ−プロピル基、ｉｓｏ−プロピル基、シクロプロピル基、ｎ−ブチル基、ｉｓｏ−ブチル基、ｔ−ブチル基、シクロブチル基、ペンチル基、ｉｓｏ−ペンチル基、ｎｅｏ−ペンチル基、シクロペンチル基、ヘキシル基、シクロヘキシル基、メチルシクロヘキシル基、シクロヘキセニル基、シクロヘキサジエニル基、メンチル基、ピナニル基、ビシクロヘプチル（ノルボニル）基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基が挙げられる。アラルキル基又はアリールの例としては、１-フェニルエチル基、２-フェニルエチル基、２−メチルフェニル基、３−メチルフェニル基、４−メチルフェニル基、ベンジル基、フェニル基、キシリル基、メシチル基、クミル基、１−ナフチル基、２−ナフチル基等が挙げられる。アルキロキシカルボニル基、アルキルカルボニロキシ基、アルキルカルボニル基としては、前述のアルキル基にそれぞれオキシカルボニル基、カルボニロキシ基、カルボニル基が結合した基が挙げられる。
Ar1およびAr2のベンゼン環が縮環した芳香族炭化水素基の置換基として好ましくはアルコキシ基、アラルキロキシ基又はアリーロキシ基であり、より好ましくはアルコキシ基であり、さらに好ましくはメトキシ基である。
As the substituent of the aromatic hydrocarbon group in which the benzene rings of Ar 1 and Ar 2 are condensed, a group consisting of a carbon atom, a hydrogen atom and an oxygen atom is preferable, preferably having 1 to 20 carbon atoms, more preferably 1-12 alkoxy groups, preferably 7-19 carbon atoms, more preferably 7-11 aralkyloxy groups, preferably 6-18 carbon atoms, more preferably 6-10 aryloxy groups, hydroxyl groups, Preferably an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, preferably 6 to 18 carbon atoms, more preferably 6 to 10 aryl groups, preferably 7 to 19 carbon atoms, More preferably 7 to 11 aralkyl groups, preferably 2 to 21 carbon atoms, more preferably 2 to 13 alkyloxycarbonyl groups, preferably 2 to 21 carbon atoms, Ri preferably alkylcarbonyloxy groups 2 to 13, preferably from 2 to 21 carbon atoms, more preferably an alkylcarbonyl group or a 2-13, and the like aldehyde group.
Specific examples of the alkoxy group, the aralkyloxy group, and the aryloxy group include a methoxy group, an ethoxy group, an n-propyloxy group, an iso-propyloxy group, a cyclopropyloxy group, an n-butyroxy group, an iso-butyroxy group, a t-butyroxy group, Cyclobutyroxy, pentyloxy, iso-pentyloxy, neo-pentyloxy, cyclopentyloxy, hexyloxy, cyclohexyloxy, methylcyclohexyloxy, cyclohexenyloxy, cyclohexadienyloxy, menthyloxy, pinanyloxy Group, bicycloheptyloxy (norbornyloxy) group, octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group, 1-phenylethoxy group, 2-phenylethyloxy group, 2-methylphenyloxy group, 3- Chirufenirokishi group, 4-methyl-phenylene b alkoxy group, benzyloxy group, phenyloxy group, Kishirirokishi group, Meshichirokishi group, Kumirokishi group, 1-naphthyloxy group, 2-naphthyloxy group and the like. Examples of alkyl groups include methyl, ethyl, n-propyl, iso-propyl, cyclopropyl, n-butyl, iso-butyl, t-butyl, cyclobutyl, pentyl, iso-pentyl. Group, neo-pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, methylcyclohexyl group, cyclohexenyl group, cyclohexadienyl group, menthyl group, pinanyl group, bicycloheptyl (norbornyl) group, octyl group, nonyl group, decyl group , Undecyl group and dodecyl group. Examples of aralkyl group or aryl include 1-phenylethyl group, 2-phenylethyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, benzyl group, phenyl group, xylyl group, mesityl group , Cumyl group, 1-naphthyl group, 2-naphthyl group and the like. Examples of the alkyloxycarbonyl group, the alkylcarbonyloxy group, and the alkylcarbonyl group include groups in which an oxycarbonyl group, a carbonyloxy group, and a carbonyl group are bonded to the aforementioned alkyl group, respectively.
The substituent of the aromatic hydrocarbon group in which the benzene rings of Ar 1 and Ar 2 are condensed is preferably an alkoxy group, an aralkyloxy group or an aryloxy group, more preferably an alkoxy group, and further preferably a methoxy group.
上述の一般式（Ｉ）において、R1およびR2の炭化水素基としては好ましくは炭素原子数１〜２０、より好ましくは１〜１２のアルキル基、好ましくは炭素原子数７〜１９、より好ましくは７〜１１のアラルキル基又は好ましくは炭素原子数６〜１８、より好ましくは６〜１０のアリール基が挙げられる。アルキル基の例としてはメチル基、エチル基、ｎ−プロピル基、ｉｓｏ−プロピル基、シクロプロピル基、ｎ−ブチル基、ｉｓｏ−ブチル基、ｔ−ブチル基、シクロブチル基、ペンチル基、ｉｓｏ−ペンチル基、ｎｅｏ−ペンチル基、シクロペンチル基、ヘキシル基、シクロヘキシル基、メチルシクロヘキシル基、シクロヘキセニル基、シクロヘキサジエニル基、メンチル基、ピナニル基、ビシクロヘプチル（ノルボニル）基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基が挙げられる。アラルキル基又はアリールの例としては、１-フェニルエチル基、２-フェニルエチル基、２−メチルフェニル基、３−メチルフェニル基、４−メチルフェニル基、ベンジル基、フェニル基、キシリル基、メシチル基、クミル基、１−ナフチル基、２−ナフチル基等が挙げられる。Ｒ１およびＲ２のアルキル基、アラルキル基、アリール基の置換基としては前述のＡｒ１およびＡｒ２のベンゼン環が縮環した芳香族炭化水素基の置換基の具体例および好ましい例と同じである。
R1およびR2として好ましくは水素原子又は炭素原子数１〜４のアルキル基であり、より好ましくは水素原子又はメチル基であり、さらに好ましくは水素原子である。
前記のＸは、ハロゲン原子、水酸基又は−ＳＯ3Ｑで表される基（ここで、Ｑは置換されていてもよい１価の炭化水素基を表す。）である。Ｘで表されるハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられ、塩素原子、臭素原子、ヨウ素原子が好ましい。−ＳＯ3Ｑで表される基中のＱで表される１価の炭化水素基としては、前記Ｒ１およびＲ２で表される１価の炭化水素基の具体例及び好ましい例が挙げられる。このＱで表される１価の炭化水素基は、置換されていてもよく、その置換基としては、例えば、フッ素原子が挙げられる。−ＳＯ3Ｑで表される基の好ましい具体例としては、メタンスルフォネート基、ベンゼンスルフォネート基、ｐ−トルエンスルフォネート基、トリフルオロメタンスルフォネート基が挙げられる。
Ｘは、好ましくはハロゲン原子、−ＳＯ3Ｑで表される基であり、より好ましくは塩素原子、臭素原子、ヨウ素原子、−ＳＯ3Ｑで表される基であり、さらに好ましくは塩素原子、臭素原子、ヨウ素原子、トリフルオロメタンスルフォネート基であり、特に好ましくは塩素原子、臭素原子、ヨウ素原子である。
In the above general formula (I), the hydrocarbon group of R 1 and R 2 is preferably an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, preferably 7 to 19 carbon atoms, and more preferably. Is an aralkyl group having 7 to 11 carbon atoms, or preferably an aryl group having 6 to 18 carbon atoms, more preferably 6 to 10 carbon atoms. Examples of alkyl groups include methyl, ethyl, n-propyl, iso-propyl, cyclopropyl, n-butyl, iso-butyl, t-butyl, cyclobutyl, pentyl, iso-pentyl. Group, neo-pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, methylcyclohexyl group, cyclohexenyl group, cyclohexadienyl group, menthyl group, pinanyl group, bicycloheptyl (norbornyl) group, octyl group, nonyl group, decyl group , Undecyl group and dodecyl group. Examples of aralkyl group or aryl include 1-phenylethyl group, 2-phenylethyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, benzyl group, phenyl group, xylyl group, mesityl group , Cumyl group, 1-naphthyl group, 2-naphthyl group and the like. The substituents for the alkyl group, aralkyl group, and aryl group of R 1 and R 2 are the same as the specific examples and preferred examples of the substituent of the aromatic hydrocarbon group in which the benzene ring of Ar 1 and Ar 2 is condensed. is there.
R 1 and R 2 are preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group, and still more preferably a hydrogen atom.
X is a halogen atom, a hydroxyl group or a group represented by —SO 3 Q (where Q represents a monovalent hydrocarbon group which may be substituted). Examples of the halogen atom represented by X include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom, a bromine atom, and an iodine atom are preferable. Examples of the monovalent hydrocarbon group represented by Q in the group represented by —SO 3 Q include specific examples and preferred examples of the monovalent hydrocarbon group represented by R 1 and R 2. . The monovalent hydrocarbon group represented by Q may be substituted, and examples of the substituent include a fluorine atom. Preferable specific examples of the group represented by —SO 3 Q include a methane sulfonate group, a benzene sulfonate group, a p-toluene sulfonate group, and a trifluoromethane sulfonate group.
X is preferably a halogen atom or a group represented by —SO 3 Q, more preferably a chlorine atom, a bromine atom, an iodine atom or a group represented by —SO 3 Q, still more preferably a chlorine atom, A bromine atom, an iodine atom, and a trifluoromethanesulfonate group, particularly preferably a chlorine atom, a bromine atom, and an iodine atom.
上述の課題を解決するためには本発明の芳香族エーテル化合物は炭素、水素および酸素からのみ構成されている。ただし、重合後のプロセスにおいて除去可能な元素、もしくは重合体のあらゆる使用または処分において環境への影響が無視できると判断できる場合は、上記以外の元素を構成元素として含有させてもよい。 In order to solve the above-mentioned problems, the aromatic ether compound of the present invention is composed only of carbon, hydrogen and oxygen. However, if it can be determined that the element that can be removed in the post-polymerization process or the influence on the environment can be ignored in any use or disposal of the polymer, elements other than those described above may be included as constituent elements.
本発明物質の一般的な合成方法を以下に述べる。
対応するAr2OHをアルゴンガス雰囲気下で、N,N-ジメチルホルムアミド、クロロホルム等の溶媒に溶かし、冷却しながら等モル量以上の水素化ナトリウムを少しずつ加え水素ガスが発生しなくなるまで撹拌する。次いで、Ar1C(R1R2)X（Xは上記のようにハロゲン原子等。）の等モル量をN,N-ジメチルホルムアミド、クロロホルム等の溶媒に溶かし加え、反応が終了するまで撹拌する。反応が進行しないようなら還流させる。反応終了後、脱イオン水で洗浄し適切な溶媒で抽出を行う。無水硫酸マグネシウム等で乾燥させた後、減圧下で濃縮すると粗結晶が得られる。シリカゲルカラムおよび再結晶等により精製を行う。
A general synthesis method of the substance of the present invention is described below.
Dissolve the corresponding Ar 2 OH in an argon gas atmosphere in a solvent such as N, N-dimethylformamide or chloroform, and gradually add an equimolar amount or more of sodium hydride while cooling until stirring stops. . Next, an equimolar amount of Ar 1 C (R 1 R 2 ) X (X is a halogen atom or the like as described above) is dissolved in a solvent such as N, N-dimethylformamide or chloroform, and stirred until the reaction is completed. To do. If the reaction does not proceed, reflux. After the reaction is complete, wash with deionized water and extract with a suitable solvent. After drying with anhydrous magnesium sulfate or the like, a crude crystal is obtained by concentration under reduced pressure. Purification is performed using a silica gel column and recrystallization.
本発明の光重合開始剤は、イオン重合、ラジカル重合などの開始剤として有用であり、特にイオン重合、とりわけカチオン重合の開始剤として好適である。本発明の光重合開始剤による光重合しうるモノマーの種類としては、エポキシ化合物、ビニルエーテル化合物、ビニル化合物、環状エーテル化合物等が挙げられる。 The photopolymerization initiator of the present invention is useful as an initiator for ionic polymerization and radical polymerization, and is particularly suitable as an initiator for ionic polymerization, particularly cationic polymerization. Examples of the monomer that can be photopolymerized by the photopolymerization initiator of the present invention include epoxy compounds, vinyl ether compounds, vinyl compounds, and cyclic ether compounds.
以下に、実施例に基づいて本発明を更に詳細に説明するが、本発明はこれらの実施例により限定されるものではない。
下記化合物１〜４を以下に述べるようにして合成した。
Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.
The following compounds 1 to 4 were synthesized as described below.
実施例１
（ｉ）1-(4-メトキシベンジルオキシ)アントラセン（化合物１）（比較化合物）の合成
1-ヒドロキシアントラセン(Tetrahedron Lett. 44, 1215-1219(2003)参照。)0.50 g(2.59 mmol)をアルゴンガス雰囲気下でN,N-ジメチルホルムアミド10mlに溶かし、氷冷しながら水素化ナトリウム(純度60%)0.15 g(3.89 mmol)を少量ずつ加え、水素ガスが発生しなくなるまで撹拌した。次いで、4-メトキシベンジルクロリド0.41 g(2.59 mmol)を加え、室温で約2時間撹拌を行った。攪拌終了後、脱イオン水 200 ml(50 ml×4回)で洗浄し、酢酸エチル75 ml(25 ml×3回)で抽出を行った。無水硫酸マグネシウムで乾燥させた後、減圧下で濃縮し粗結晶を得た。シリカゲルカラム(展開溶媒：クロロホルム)により予備精製を行なった後、酢酸エチルを用いた再結晶により精製した。収量：0.59 g 収率：73.4 %
以下の試験結果より上記の化合物１であることを確認した。
＜１＞1H-NMR (ppm/600MHz, CDCl3)3.85 (3H,s), 5.23 (2H, s), 6.81 (1H, d), 7.00 (2H, d), 7.35 (1H, dd) , 7.44 (2H, m), 7.51 (2H, d), 7.59 (1H, d), 7.98 (1H, d), 8.02 (1H, d), 8.37 (1H, s), 8.87 (1H, s)
＜２＞13C-NMR (ppm/150MHz, CDCl3)68.9, 103.0, 120.9, 121.3, 123.9, 125.1, 125.2, 125.6, 126.0, 126.5, 126.7, 127.8, 128.7, 128.8, 129.1, 131.2, 131.8, 132.4, 132.7, 133.8, 154.7.
＜３＞IR(cm-1/KBr)：1248(C‐O)
＜４＞融点：108.0-109.0℃
Example 1
(I) Synthesis of 1- (4-methoxybenzyloxy) anthracene (Compound 1) (Comparative Compound)
1-Hydroxyanthracene (see Tetrahedron Lett. 44, 1215-1219 (2003)) 0.50 g (2.59 mmol) was dissolved in 10 ml of N, N-dimethylformamide under an argon gas atmosphere and sodium hydride (purity) 60%) 0.15 g (3.89 mmol) was added in small portions and stirred until no hydrogen gas was generated. Next, 0.41 g (2.59 mmol) of 4-methoxybenzyl chloride was added, and the mixture was stirred at room temperature for about 2 hours. After completion of stirring, the mixture was washed with 200 ml of deionized water (50 ml × 4 times) and extracted with 75 ml of ethyl acetate (25 ml × 3 times). After drying over anhydrous magnesium sulfate, it was concentrated under reduced pressure to obtain crude crystals. Preliminary purification was performed with a silica gel column (developing solvent: chloroform), and then purification was performed by recrystallization using ethyl acetate. Yield: 0.59 g Yield: 73.4%
From the following test results, it was confirmed to be Compound 1 above.
<1> 1 H-NMR (ppm / 600 MHz, CDCl 3 ) 3.85 (3H, s), 5.23 (2H, s), 6.81 (1H, d), 7.00 (2H, d), 7.35 (1H, dd), 7.44 (2H, m), 7.51 (2H, d), 7.59 (1H, d), 7.98 (1H, d), 8.02 (1H, d), 8.37 (1H, s), 8.87 (1H, s)
<2> 13 C-NMR (ppm / 150 MHz, CDCl 3 ) 68.9, 103.0, 120.9, 121.3, 123.9, 125.1, 125.2, 125.6, 126.0, 126.5, 126.7, 127.8, 128.7, 128.8, 129.1, 131.2, 131.8, 132.4 , 132.7, 133.8, 154.7.
<3> IR (cm -1 / KBr): 1248 (CO)
<4> Melting point: 108.0-109.0 ° C
（ｉｉ）1-(1-ナフチルメチルオキシ)アントラセン（化合物２）の合成
1-ヒドロキシアントラセン(Tetrahedron Lett. 44, 1215-1219(2003)参照。)0.45 g(2.33 mmol)をアルゴンガス雰囲気下でN,N-ジメチルホルムアミド10mlに溶かし、氷冷しながら水素化ナトリウム(純度60%)0.14g(3.50mmol)を少量ずつ加え、水素ガスが発生しなくなるまで撹拌した。次いで、1-クロロメチル-ナフタレン0.38g(2.33mmol)をN,N-ジメチルホルムアミド1 mlに溶かし加え、室温で約3 h撹拌を行った。攪拌終了後、脱イオン水200ml(50ml×4回)で洗浄し、酢酸エチル75 ml(25 ml×3回)で抽出を行った。無水硫酸マグネシウムで乾燥させた後、減圧下で濃縮し粗結晶を得た。シリカゲルカラム(展開溶媒：クロロホルム)により予備精製を行なった後、酢酸エチルを用いた再結晶により精製した。
以下のデータより目的とする芳香族エーテル化合物（化合物２）であることを同定した。収量：0.56g、収率：71.8%
＜１＞1H-NMR (ppm/600MHz, CDCl3) 5.75(2H, s), 6.98 (1H, d), 7.25−7.45 (3H, m), 7.53−7.56 (3H, m), 7.64 (1H, d), 7.76 (1H, d), 7.92−7.98 (4H, m), 8.18(1H, d), 8.39(1H, s), 8.82 (1H, s)
＜２＞13C-NMR (ppm/150MHz, CDCl3) 68.9, 103.0, 120.9, 121.3, 123.9, 125.1, 125.2, 125.4, 125.7(2C), 126.0, 126.5, 126.7, 127.8, 128.7, 128.8, 129.1, 131.2, 131.8, 132.0, 132.4, 132.7, 133.8, 154.7.
＜３＞IR(cm-1/KBr)：1260(C‐O)
＜４＞元素分析 (C25H18O) 計算値C(89.79%)、H(5.43%)/ 測定値C(89.89%)、H(5.87%)
＜５＞融点：129.2−130.0℃
(Ii) Synthesis of 1- (1-naphthylmethyloxy) anthracene (Compound 2)
1-Hydroxyanthracene (see Tetrahedron Lett. 44, 1215-1219 (2003)) 0.45 g (2.33 mmol) was dissolved in 10 ml of N, N-dimethylformamide under an argon gas atmosphere, and sodium hydride (purity) 60%) 0.14 g (3.50 mmol) was added in small portions and stirred until no hydrogen gas was generated. Subsequently, 0.38 g (2.33 mmol) of 1-chloromethyl-naphthalene was dissolved in 1 ml of N, N-dimethylformamide and stirred at room temperature for about 3 hours. After stirring, the mixture was washed with 200 ml of deionized water (50 ml × 4 times) and extracted with 75 ml of ethyl acetate (25 ml × 3 times). After drying over anhydrous magnesium sulfate, it was concentrated under reduced pressure to obtain crude crystals. Preliminary purification was performed with a silica gel column (developing solvent: chloroform), and then purification was performed by recrystallization using ethyl acetate.
From the following data, it identified that it was the target aromatic ether compound (compound 2). Yield: 0.56g, Yield: 71.8%
<1> 1 H-NMR (ppm / 600 MHz, CDCl 3 ) 5.75 (2H, s), 6.98 (1H, d), 7.25-7.45 (3H, m), 7.53-7.56 (3H, m), 7.64 (1H , d), 7.76 (1H, d), 7.92-7.98 (4H, m), 8.18 (1H, d), 8.39 (1H, s), 8.82 (1H, s)
<2> 13 C-NMR (ppm / 150 MHz, CDCl 3 ) 68.9, 103.0, 120.9, 121.3, 123.9, 125.1, 125.2, 125.4, 125.7 (2C), 126.0, 126.5, 126.7, 127.8, 128.7, 128.8, 129.1, 131.2, 131.8, 132.0, 132.4, 132.7, 133.8, 154.7.
<3> IR (cm -1 / KBr): 1260 (C-O)
<4> Elemental analysis (C 25 H 18 O) Calculated value C (89.79%), H (5.43%) / Measured value C (89.89%), H (5.87%)
<5> Melting point: 129.2-130.0 ° C
（iii）1-(2-メチル-1-ナフチルメチルオキシ)アントラセン（化合物３）の合成
1-ヒドロキシアントラセン(Tetrahedron Lett. 44, 1215-1219(2003)参照。)0.30g(1.55mmol)をアルゴンガス雰囲気下でN,N-ジメチルホルムアミド10mlに溶かし、氷冷しながら水素化ナトリウム(純度60%)0.09g(2.3mmol)を少量ずつ加え、水素ガスが発生しなくなるまで撹拌した。次いで、1-クロロメチル-2-メチルナフタレン0.29g(1.55mmol)をN,N-ジメチルホルムアミド1 mlに溶かし加え、室温で約3時間撹拌を行った。攪拌終了後、脱イオン水 200 ml(50 ml×4回)で洗浄し、酢酸エチル75ml(25ml×3回)で抽出を行った。無水硫酸マグネシウムで乾燥させた後、減圧下で濃縮し粗結晶を得た。シリカゲルカラム(展開溶媒：クロロホルム)により予備精製を行なった後、酢酸エチルを用いた再結晶により精製した。収量：0.35g 収率：64.8 %
以下のデータより目的とする芳香族エーテル化合物であることを同定した。
＜１＞1H-NMR (ppm/600MHz, CDCl3) 2.70 (3H,s), 5.71 (2H, s), 7.08 (1H, d), 7.36 (1H, d), 7.40−7.48 (5H, m) , 7.66 (1H, d), 7.84−7.96 (4H, m), 8.15(1H, d), 8.38(1H, s), 8.68 (1H, s)
＜２＞13C-NMR (ppm/150MHz, CDCl3) 64.0, 102.6, 120.8, 121.4, 123.8, 125.0, 125.1, 125.3, 125.5, 125.6, 126.7(2C), 127.8, 128.4, 128.8, 129.1, 129.1, 129.2, 131.2, 132.0, 132.5, 132.7, 133.2, 136.1, 155.2.
＜３＞IR(cm-1/KBr)：1257(C‐O)
＜４＞元素分析 (C26H20O) 計算値C(89.62%)、H(5.79%)/ 測定値C(89.19%)、H(5.88%)
＜５＞融点：180.5-181.7℃
(Iii) Synthesis of 1- (2-methyl-1-naphthylmethyloxy) anthracene (compound 3)
1-Hydroxyanthracene (see Tetrahedron Lett. 44, 1215-1219 (2003)) 0.30 g (1.55 mmol) was dissolved in 10 ml of N, N-dimethylformamide under an argon gas atmosphere, and sodium hydride (purity) 60%) 0.09 g (2.3 mmol) was added in small portions and stirred until no hydrogen gas was generated. Next, 0.29 g (1.55 mmol) of 1-chloromethyl-2-methylnaphthalene was dissolved in 1 ml of N, N-dimethylformamide and stirred at room temperature for about 3 hours. After stirring, the mixture was washed with 200 ml of deionized water (50 ml × 4 times) and extracted with 75 ml of ethyl acetate (25 ml × 3 times). After drying over anhydrous magnesium sulfate, it was concentrated under reduced pressure to obtain crude crystals. Preliminary purification was performed with a silica gel column (developing solvent: chloroform), and then purification was performed by recrystallization using ethyl acetate. Yield: 0.35g Yield: 64.8%
From the following data, it was identified as the target aromatic ether compound.
<1> 1 H-NMR (ppm / 600 MHz, CDCl 3 ) 2.70 (3H, s), 5.71 (2H, s), 7.08 (1H, d), 7.36 (1H, d), 7.40-7.48 (5H, m ), 7.66 (1H, d), 7.84-7.96 (4H, m), 8.15 (1H, d), 8.38 (1H, s), 8.68 (1H, s)
<2> 13 C-NMR (ppm / 150 MHz, CDCl 3 ) 64.0, 102.6, 120.8, 121.4, 123.8, 125.0, 125.1, 125.3, 125.5, 125.6, 126.7 (2C), 127.8, 128.4, 128.8, 129.1, 129.1, 129.2, 131.2, 132.0, 132.5, 132.7, 133.2, 136.1, 155.2.
<3> IR (cm -1 / KBr): 1257 (CO)
<4> Elemental analysis (C 26 H 20 O) Calculated value C (89.62%), H (5.79%) / Measured value C (89.19%), H (5.88%)
<5> Melting point: 180.5-181.7 ° C
（ｉｖ）1-(2-メトキシ-1-ナフチルメチルオキシ)アントラセン（化合物４）の合成
1-ヒドロキシアントラセン(Tetrahedron Lett. 44, 1215-1219(2003)参照。)0.40g(2.07mmol)をアルゴンガス雰囲気下でN,N-ジメチルホルムアミド10mlに溶かし、氷冷しながら水素化ナトリウム(純度60%)0.12g(3.10mmol)を少量ずつ加え、水素ガスが発生しなくなるまで撹拌した。次いで、1-クロロメチル-2-メトキシナフタレン0.42g(2.07mmol)をN,N-ジメチルホルムアミド1 mlに溶かし加え、室温で約3時間撹拌を行った。攪拌終了後、脱イオン水200 ml(50ml×4回)で洗浄し、酢酸エチル75ml(25ml×3回)で抽出を行った。無水硫酸マグネシウムで乾燥させた後、減圧下で濃縮し粗結晶を得た。シリカゲルカラム(展開溶媒：クロロホルム)により予備精製を行なった後、酢酸エチルを用いた再結晶により精製した。収量：0.66 g 収率：65 %
以下のデータより目的とする芳香族エーテル化合物であることを同定した。
＜１＞1H-NMR (ppm/600MHz, CDCl3) 4.01 (3H, s), 5.80 (2H, s), 7.11 (1H, d), 7.33−7.48 (6H, m) , 7.61 (1H, d), 7.85−7.96 (4H, m), 8.15(1H, d), 8.38(1H, s), 8.68 (1H, s)
＜２＞13C-NMR (ppm/150MHz, CDCl3) 56.9, 61.2, 102.9, 113.4, 117.2, 120.5, 121.5, 123.5, 123.8, 123.9, 124.9, 125.3, 125.4, 125.4, 125.5, 127.1, 127.8, 128.3, 128.8, 129.2, 130.9, 131.9, 132.7, 134.1, 155.6.
＜３＞IR(cm-1/KBr)：1257(C‐O)
＜４＞元素分析 (C22H18O2) 計算値C(85.20%)、H(5.51%)/ 測定値C(85.69%)、H(5.53%)
＜５＞融点：144.0-145.2℃
(Iv) Synthesis of 1- (2-methoxy-1-naphthylmethyloxy) anthracene (compound 4)
1-Hydroxyanthracene (see Tetrahedron Lett. 44, 1215-1219 (2003)) 0.40 g (2.07 mmol) was dissolved in 10 ml of N, N-dimethylformamide under an argon gas atmosphere and sodium hydride (purity) with ice cooling. 60%) 0.12 g (3.10 mmol) was added in small portions and stirred until no hydrogen gas was generated. Next, 0.42 g (2.07 mmol) of 1-chloromethyl-2-methoxynaphthalene was dissolved in 1 ml of N, N-dimethylformamide and stirred at room temperature for about 3 hours. After stirring, the mixture was washed with 200 ml of deionized water (50 ml × 4 times) and extracted with 75 ml of ethyl acetate (25 ml × 3 times). After drying over anhydrous magnesium sulfate, it was concentrated under reduced pressure to obtain crude crystals. Preliminary purification was performed with a silica gel column (developing solvent: chloroform), and then purification was performed by recrystallization using ethyl acetate. Yield: 0.66 g Yield: 65%
From the following data, it was identified as the target aromatic ether compound.
<1> 1 H-NMR (ppm / 600 MHz, CDCl3) 4.01 (3H, s), 5.80 (2H, s), 7.11 (1H, d), 7.33-7.48 (6H, m), 7.61 (1H, d) , 7.85-7.96 (4H, m), 8.15 (1H, d), 8.38 (1H, s), 8.68 (1H, s)
<2> 13 C-NMR (ppm / 150 MHz, CDCl3) 56.9, 61.2, 102.9, 113.4, 117.2, 120.5, 121.5, 123.5, 123.8, 123.9, 124.9, 125.3, 125.4, 125.4, 125.5, 127.1, 127.8, 128.3, 128.8, 129.2, 130.9, 131.9, 132.7, 134.1, 155.6.
<3> IR (cm -1 / KBr): 1257 (CO)
<4> Elemental analysis (C 22 H 18 O 2 ) Calculated value C (85.20%), H (5.51%) / Measured value C (85.69%), H (5.53%)
<5> Melting point: 144.0-145.2 ° C
実施例２
（ｖ）化合物１〜４を用いたシクロヘキセンオキシドの光重合
実施例１の(i)〜(iv)で合成した化合物１〜４を、蒸留精製したシクロヘキセンオキシドに0.2mol%で加え、コック付き反応管内で凍結-脱気-融解を三回繰り返した後に60℃で撹拌しながら、500W超高圧水銀灯からの340nmよりも長波長の光(3.0mW cm-2)を８時間または１６時間照射した。反応を下記反応式で示した。照射後、反応液をメタノールに注ぎ生成高分子を沈殿させ、ろ過および真空乾燥（40℃）させてポリ(シクロヘキセンオキシド)を得た。重合結果を表１に示す。
Example 2
(V) Photopolymerization of cyclohexene oxide using compounds 1 to 4 Compounds 1 to 4 synthesized in (i) to (iv) of Example 1 were added at 0.2 mol% to distilled and purified cyclohexene oxide, and a reaction with a cock was made. The tube was irradiated with light having a wavelength longer than 340 nm (3.0 mW cm −2 ) from a 500 W ultrahigh pressure mercury lamp for 8 hours or 16 hours while stirring at 60 ° C. after repeating freeze-degas-thaw three times in the tube. The reaction was shown by the following reaction formula. After irradiation, the reaction solution was poured into methanol to precipitate the produced polymer, followed by filtration and vacuum drying (40 ° C.) to obtain poly (cyclohexene oxide). The polymerization results are shown in Table 1.
上記表１の結果より、本発明の化合物２，３及び４は、比較の化合物１に比べ光重合開始剤として優れた作用を示すことが分かる。
From the results shown in Table 1, it can be seen that the compounds 2, 3 and 4 of the present invention show an excellent action as a photopolymerization initiator as compared with the comparative compound 1.
Claims (3)
一般式（Ｉ）
Formula (I)
2. A process for producing an aromatic ether compound represented by the general formula (I) according to claim 1, wherein Ar 2 OH and Ar 1 C (R 1 R 2 ) X are reacted (wherein Ar 1 , Ar 2 , R 1 and R 2 have the same meaning as described above, X is a halogen atom, a hydroxyl group or a group represented by —SO 3 Q (where Q is an optionally substituted monovalent hydrocarbon) Group).
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50106950A (en) * | 1974-02-04 | 1975-08-22 | ||
| JPS597958A (en) * | 1982-07-07 | 1984-01-17 | Asahi Chem Ind Co Ltd | Novel electrophotographic receptor |
| JPS59133095A (en) * | 1983-01-21 | 1984-07-31 | Oji Paper Co Ltd | Heat-sensitive recording paper |
| JPH06157389A (en) * | 1992-06-06 | 1994-06-03 | Basf Ag | Preparation of beta-naphthyl benzyl ether |
| JPH10147608A (en) * | 1996-09-19 | 1998-06-02 | Nippon Soda Co Ltd | Photocatalyst composition |
| JP2000344704A (en) * | 1999-01-29 | 2000-12-12 | Nippon Kayaku Co Ltd | New anthracene compound, resin composition containing the compound and production of 9,10-dietherified anthracene derivative |
| JP2002302507A (en) * | 2001-01-31 | 2002-10-18 | Nippon Soda Co Ltd | Photocurable composition containing iodonium salt compound |
| JP2003313546A (en) * | 2002-04-24 | 2003-11-06 | Tokuyama Corp | Luminescent composition |
-
2006
- 2006-02-15 JP JP2006038511A patent/JP5027424B2/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50106950A (en) * | 1974-02-04 | 1975-08-22 | ||
| JPS597958A (en) * | 1982-07-07 | 1984-01-17 | Asahi Chem Ind Co Ltd | Novel electrophotographic receptor |
| JPS59133095A (en) * | 1983-01-21 | 1984-07-31 | Oji Paper Co Ltd | Heat-sensitive recording paper |
| JPH06157389A (en) * | 1992-06-06 | 1994-06-03 | Basf Ag | Preparation of beta-naphthyl benzyl ether |
| JPH10147608A (en) * | 1996-09-19 | 1998-06-02 | Nippon Soda Co Ltd | Photocatalyst composition |
| JP2000344704A (en) * | 1999-01-29 | 2000-12-12 | Nippon Kayaku Co Ltd | New anthracene compound, resin composition containing the compound and production of 9,10-dietherified anthracene derivative |
| JP2002302507A (en) * | 2001-01-31 | 2002-10-18 | Nippon Soda Co Ltd | Photocurable composition containing iodonium salt compound |
| JP2003313546A (en) * | 2002-04-24 | 2003-11-06 | Tokuyama Corp | Luminescent composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5027424B2 (en) | 2012-09-19 |
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