JPS6230209B2 - - Google Patents
Info
- Publication number
- JPS6230209B2 JPS6230209B2 JP56054579A JP5457981A JPS6230209B2 JP S6230209 B2 JPS6230209 B2 JP S6230209B2 JP 56054579 A JP56054579 A JP 56054579A JP 5457981 A JP5457981 A JP 5457981A JP S6230209 B2 JPS6230209 B2 JP S6230209B2
- Authority
- JP
- Japan
- Prior art keywords
- phenylacetylene
- electron
- copolymer
- compound
- present
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Description
【発明の詳細な説明】
本発明はフエニルアセチレン系共重合体の製造
方法に関するものである。さらに詳しくいうと、
本発明は電子供与性の置換基を有するフエニルア
セチレン化合物と電子吸引性の置換基を有するフ
エニルアセチレン化合物とを接触状態に維持し
て、ガンマ線、紫外線などの活性線を照射する
か、熱を加えることによつて共重合させることを
特徴とするフエニルアセチレン系共重合体の製造
方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a phenylacetylene copolymer. To be more specific,
The present invention involves maintaining a phenylacetylene compound having an electron-donating substituent and a phenylacetylene compound having an electron-withdrawing substituent in contact with each other, and irradiating the compound with active rays such as gamma rays and ultraviolet rays, or by applying heat. The present invention relates to a method for producing a phenylacetylene copolymer, characterized in that copolymerization is carried out by adding a phenylacetylene copolymer.
フエニルアセチレン化合物の重合によつて生成
する重合体は、共役２重結合が連なつたポリエン
構造をもつため、高分子半導体として利用するこ
とが期待されている。しかし、フエニルアセチレ
ン化合物のように３重結合での付加反応によつて
重合する化合物は一般に重合が困難であるため、
高価で取扱いの難しいイオン重合触媒を用いる
か、あるいは、150℃程度またはそれ以上の高温
で熱重合する方法が用いられているが、重合度の
低いものしか得られないのが現状である。本発明
者らは、重合度の高いフエニルアセチレン系重合
体を速やかに得る方法について鋭意研究を重ねた
結果、電子供与性の置換基を有するフエニルアセ
チレン化合物と反対の性質をもつた電子吸引性置
換基を有するフエニルアセチレン化合物とを接触
状態に維持して、活性線を照射するか、加熱して
共重合させることによつて、長い共役２重結合を
もつたフエニルアセチレン系共重合体を速やかに
得ることができることを見出し本発明をなすに至
つた。 Polymers produced by polymerization of phenylacetylene compounds have a polyene structure with a series of conjugated double bonds, and are therefore expected to be used as polymeric semiconductors. However, compounds that polymerize through addition reactions at triple bonds, such as phenylacetylene compounds, are generally difficult to polymerize.
Methods that use expensive and difficult-to-handle ionic polymerization catalysts or thermal polymerization at high temperatures of around 150°C or higher are currently used, but currently only products with a low degree of polymerization can be obtained. As a result of intensive research into a method for rapidly obtaining a phenylacetylene polymer with a high degree of polymerization, the present inventors discovered that a phenylacetylene compound having an electron-donating substituent has an electron-withdrawing property that is opposite to that of a phenylacetylene compound having an electron-donating substituent. A phenylacetylene copolymer having a long conjugated double bond can be produced by maintaining the phenylacetylene compound having a conjugated double bond in contact with the phenylacetylene compound and copolymerizing it by irradiating it with actinic rays or by heating it. The present inventors have discovered that coalescence can be rapidly obtained and have completed the present invention.
本発明の好ましい実施の態様について詳述すれ
ば、次の通りである。まず精製した電子供与性の
置換基を有するフエニルアセチレン化合物と電子
吸引性の置換基を有するフエニルアセチレン化合
物とをガラス製または石英製の反応管に入れ、さ
らに必要ならばテトラヒドロフランを加えて、反
応管を真空系に接続し、反応管の底部を液体窒素
により冷却して、凍結排気する。また、溶媒を用
いる場合には溶解、脱気を２回くり返す操作を追
加する。そののち、反応管を減圧下で封ずる。こ
れをガンマ線、紫外線などの活性線照射装置を用
いて所定時間照射するか、120℃程度またはそれ
以上の温度で熱重合したのち、開管し、これに水
−メタノールの混合液を加えて、生成した共重合
体を沈殿させ、遠心分離して、フエニルアセチレ
ン系共重合体を得る。 Preferred embodiments of the present invention will be detailed as follows. First, a purified phenylacetylene compound having an electron-donating substituent and a phenylacetylene compound having an electron-withdrawing substituent are placed in a glass or quartz reaction tube, and if necessary, tetrahydrofuran is added. The reaction tube is connected to a vacuum system, and the bottom of the reaction tube is cooled with liquid nitrogen to freeze and exhaust. Moreover, when a solvent is used, an operation of repeating dissolution and deaeration twice is added. Thereafter, the reaction tube is sealed under reduced pressure. This is irradiated for a predetermined time using an active ray irradiation device such as gamma rays or ultraviolet rays, or thermally polymerized at a temperature of about 120°C or higher, then opened, and a water-methanol mixture is added to it. The produced copolymer is precipitated and centrifuged to obtain a phenylacetylene copolymer.
ここに用いる電子供与性の置換基を有するフエ
ニルアセチレン化合物としては、芳香族環のオル
ト−またはメタ−またはパラ−位に電子供与性置
換基を有するアミノフエニルアセチレン、ジメチ
ルアミノフエニルアセチレン、メトキシ−または
エトキシフエニルアセチレン、アルキルフエニル
アセチレンなどがある。また電子吸引性の置換基
を有するフエニルアセチレン化合物としては、芳
香族環のオルト−またはメタ−またはパラ−位に
電子吸引性の置換基を有するハロゲン化フエニル
アセチレン、ニトロフエニルアセチレン、シアノ
フエニルアセチレン、カルボキシフエニルアセチ
レンなどがある。 Examples of the phenylacetylene compound having an electron-donating substituent used here include aminophenylacetylene, dimethylaminophenylacetylene, and dimethylaminophenylacetylene having an electron-donating substituent at the ortho-, meta-, or para-position of the aromatic ring. Examples include methoxy- or ethoxyphenylacetylene, alkylphenylacetylene, and the like. Examples of phenylacetylene compounds having an electron-withdrawing substituent include halogenated phenylacetylene, nitrophenylacetylene, and cyanophenylacetylene having an electron-withdrawing substituent at the ortho-, meta-, or para-position of the aromatic ring. Examples include phenylacetylene and carboxyphenylacetylene.
本発明の方法において、２種の単量体を混合
し、溶媒を加えるか、または温度を上げて液体の
状態にした場合には着色が見られたが、この現象
は紫外および可視部の吸収スペクトルを調べた結
果、２種の単量体の間で電荷移動錯体が生成して
いることによることが明らかになつた。本発明の
方法による共重合の速度は、それぞれの単量体の
単独の重合速度より大きく、また、得られた共重
合体の分子量は、単独の重合体の分子量より大き
かつたが、これは、上記のような電荷移動錯体の
生成によるものと推定される。 In the method of the present invention, coloring was observed when two types of monomers were mixed and made into a liquid state by adding a solvent or raising the temperature, but this phenomenon was caused by absorption in the ultraviolet and visible regions. As a result of examining the spectrum, it became clear that this was due to the formation of a charge transfer complex between two types of monomers. The rate of copolymerization by the method of the present invention was higher than the rate of polymerization of each monomer alone, and the molecular weight of the resulting copolymer was higher than that of the individual polymers; , it is presumed that this is due to the formation of a charge transfer complex as described above.
本発明の方法によつて得られるフエニルアセチ
レン系共重合体は、２種の単量体のアセチレン基
の３重結合の位置で付加し、共重合して得られた
ものであるため、共役２重結合が多数連なつたポ
リエン構造の主鎖をもち、電気的に高分子半導体
としての性質をもつている。 The phenylacetylene copolymer obtained by the method of the present invention is obtained by adding the acetylene groups of two monomers at the triple bond position and copolymerizing them. It has a polyene structure main chain with many double bonds, and has electrical properties as a polymer semiconductor.
従つて、本発明の方法を用いることによつて、
光電材料、導電性成形体として有用なフエニルア
セチレン系高分子半導体を安価に、かつ容易に製
造することが可能である。 Therefore, by using the method of the present invention,
It is possible to inexpensively and easily produce a phenylacetylene polymer semiconductor useful as a photoelectric material and a conductive molded body.
次に実施例によつて、本発明をさらに詳細に説
明する。 Next, the present invention will be explained in more detail with reference to Examples.
実施例 １
精製したｐ−アミノフエニルアセチレン0.99ｇ
（0.0085モル）とｐ−ニトロフエニルアセチレン
1.20ｇ（0.0082モル）とをガラス製反応管中に入
れて、真空系に接続し、反応管の底部を液体窒素
で冷却しながら排気し、10-4mmHg程度の真空中
で排管した。これを140℃の恒温槽中に0.9時間浸
し、共重合反応を行なつた。反応後、反応管を開
き、生成物を水−メタノール（１：３）混合液中
に入れて共重合体を沈殿させ、遠心分離する操作
を３回くり返して共重合体をとり出し、乾燥し
て、黒褐色の共重合体0.563ｇを得た。重合率は
25.7％であつた。また、この共重合体は元素分析
の結果58.45％（モル）のニトロフエニルアセチ
レン成分を含んでいることが分かつた。Example 1 0.99 g of purified p-aminophenyl acetylene
(0.0085 mol) and p-nitrophenylacetylene
1.20 g (0.0082 mol) was placed in a glass reaction tube, connected to a vacuum system, and the bottom of the reaction tube was evacuated while being cooled with liquid nitrogen, and the tube was evacuated in a vacuum of about 10 -4 mmHg. This was immersed in a constant temperature bath at 140°C for 0.9 hours to carry out a copolymerization reaction. After the reaction, open the reaction tube, pour the product into a water-methanol (1:3) mixture to precipitate the copolymer, repeat centrifugation three times to remove the copolymer, and dry. 0.563 g of a dark brown copolymer was obtained. The polymerization rate is
It was 25.7%. Elemental analysis revealed that this copolymer contained 58.45% (mol) of nitrophenylacetylene component.
実施例 ２
精製したｐ−アミノフエニルアセチレン2.05ｇ
（0.018モル）とｐ−ニトロフエニルアセチレン
2.59ｇ（0.018モル）とを30mlのテトラヒドロフ
ランとともに石英製反応管中に入れて、真空系に
接続し、液体窒素による単量体溶液の凍結、排気
をしたのち、融解、脱気、凍結、排気を２回くり
返し封管した。これに対して、35℃で100Wの高
圧水銀灯の紫外線を５cmの距離で27.4時間照射し
て共重合反応を行なつた。反応後、実施例１と同
様の操作によつて0.187ｇの共重合体を得た。重
合率は4.03％であつた。Example 2 2.05 g of purified p-aminophenyl acetylene
(0.018 mol) and p-nitrophenylacetylene
2.59 g (0.018 mol) and 30 ml of tetrahydrofuran are placed in a quartz reaction tube, connected to a vacuum system, frozen with liquid nitrogen, evacuated, then thawed, degassed, frozen, and evacuated. The tube was sealed twice. On the other hand, a copolymerization reaction was carried out by irradiating it with ultraviolet rays from a 100 W high-pressure mercury lamp at a distance of 5 cm for 27.4 hours at 35°C. After the reaction, 0.187 g of copolymer was obtained by the same operation as in Example 1. The polymerization rate was 4.03%.
Claims (1)
レン化合物と電子吸引性の置換基を有するフエニ
ルアセチレン化合物とを、溶媒の不存在下又は溶
媒としてテトラヒドロフランの存在下で、接触状
態に維持して、活性線を照射するか熱を加えるこ
とによつて共重合させることを特徴とするフエニ
ルアセチレン系共重合体の製造方法。1. Maintaining a phenylacetylene compound having an electron-donating substituent and a phenylacetylene compound having an electron-withdrawing substituent in contact in the absence of a solvent or in the presence of tetrahydrofuran as a solvent, A method for producing a phenylacetylene copolymer, which comprises copolymerizing by irradiating with actinic rays or applying heat.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5457981A JPS57168907A (en) | 1981-04-11 | 1981-04-11 | Production of phenylacetylene copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5457981A JPS57168907A (en) | 1981-04-11 | 1981-04-11 | Production of phenylacetylene copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57168907A JPS57168907A (en) | 1982-10-18 |
| JPS6230209B2 true JPS6230209B2 (en) | 1987-07-01 |
Family
ID=12974605
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5457981A Granted JPS57168907A (en) | 1981-04-11 | 1981-04-11 | Production of phenylacetylene copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57168907A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63188609U (en) * | 1987-05-27 | 1988-12-02 |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006004161A1 (en) * | 2004-07-06 | 2006-01-12 | Kyoto University | Novel polyphenylacetylene derivatives |
| CN109912740B (en) * | 2018-06-29 | 2021-09-28 | 郑州轻工业学院 | Preparation method of polyphenylacetylene |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5740161A (en) * | 1980-08-20 | 1982-03-05 | Toyota Motor Corp | Torque transmission device including direct-coupled clutch and hydraulic torque converter |
-
1981
- 1981-04-11 JP JP5457981A patent/JPS57168907A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63188609U (en) * | 1987-05-27 | 1988-12-02 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57168907A (en) | 1982-10-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kunzler et al. | Living polymerization of aryl substituted acetylenes by MoCl5 and WCl6 based initiators: The ortho phenyl substituent effect | |
| Miao et al. | Paracyclophene Route to Poly (p-phenylenevinylene) | |
| Abbås et al. | On the thermal degradation of poly (vinyl chloride). III. Structural changes during degradation in nitrogen | |
| Naegele et al. | Polymerization of cadmium octadecylfumarate in multilayers | |
| Jenekhe et al. | Synthesis of Highly Conducting Heterocyclic F'olycarbazoles by Simultaneous Polymerization and Doping In Liquid Iodine | |
| Garton et al. | Anionic polymerization of butadiene in tetrahydrofuran. I. Isomerization of polybutadienyl salts | |
| JPS6230209B2 (en) | ||
| Ayrey et al. | Radiochemical studies of free-radical vinyl polymerizations: 7. Polymerization of methyl acrylate | |
| Hinkley et al. | Chain deformations in rubber | |
| Kojima et al. | Sorption and permeation of iodine in water‐swollen poly (vinyl alcohol) membranes and iodine complex formation | |
| JPS61235427A (en) | Formation of aromatic polymer having repeating units of arylene groups on substrate surface | |
| Kennedy et al. | Cationic polymerization with boron halides. V. Synthesis of poly (isobutylene‐b‐styrene) and poly (styrene‐b‐isobutylene) | |
| CN108623791A (en) | A kind of organic thermoelectric film material of D-A type conjugated polymer and preparation method thereof | |
| CN104650297A (en) | Preparation method of main-side chain azobenzene functional group-containing grafted copolymer | |
| Tazuke et al. | Photo and thermal polymerizations sensitized by donor–acceptor interaction. II. Photopolymerization and electronic spectroscopy of the isobutyl vinyl ether–acrylonitrile system | |
| Gratt et al. | Optical properties of block copolymers containing pendant carbazole groups and in situ synthesized CdS nanoclusters | |
| Morishima et al. | Syntheses of block copolymers of 2-methyl-2-oxazoline and aromatic vinyl compounds | |
| Villar et al. | Synthesis and Characterization of Monodisperse α, ω-Divinylpolydimethylsiloxane and ω-Vinylpolydimethylsiloxane | |
| Deffieux et al. | Anionic polymerization of ethylene oxide with cryptates as counterions: 2 | |
| Bonsall et al. | The termination step in the polymerization of methyl methacrylate at 30° C | |
| Gal et al. | Synthesis and optical properties of poly (2-ethynylpyridinum bromide) having glycidyl functionality | |
| Küçükyavuz et al. | Electrically conductive polymers from poly (N-vinylimidazole) | |
| North et al. | Role of molecular motions in polymer reactions. Part 3.—Free-radical copolymerization of methyl methacrylate with maleic anhydride and citraconic anhydride | |
| Tatarinova et al. | Oligomerization of phenylferrocenylacetylene under the action of WCl6 | |
| Hurwitz et al. | Copolymerization of di-and trifunctional arylacetylenes |