JPH0693092A - Diacetylenic polymer having double bond - Google Patents
Diacetylenic polymer having double bondInfo
- Publication number
- JPH0693092A JPH0693092A JP33384792A JP33384792A JPH0693092A JP H0693092 A JPH0693092 A JP H0693092A JP 33384792 A JP33384792 A JP 33384792A JP 33384792 A JP33384792 A JP 33384792A JP H0693092 A JPH0693092 A JP H0693092A
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- Prior art keywords
- polymer
- compound
- double bond
- group
- formula
- Prior art date
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- Polyesters Or Polycarbonates (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、精密機械やエレクトロ
ニクス分野で利用できる硬化反応性に優れた新規な架橋
性素材としての二重結合を含有するジアセチレン重合体
に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a double bond-containing diacetylene polymer as a novel crosslinkable material having excellent curing reactivity which can be used in the fields of precision machinery and electronics.
【０００２】[0002]
【従来の技術】近年、固相重合によるトポケミカル反応
を用いた単結晶ポリマーの合成は、注目されており、こ
の手法を用いて、種々の高弾性率を有する高結晶性高分
子の開発が試みられている。（例えば、「有機非線形光
学材料」、シーエムシー（１９８５）、マクロモレキュ
ル ケミストリー 第１３４巻、第２１９頁（１９７
０）、ジャーナル オブ ポリマー サイエンス 第Ｂ
９巻、第１３３頁（１９７１）、ジャーナル オブ ポ
リマー サイエンス ポリマー フィジクスエディショ
ン 第１２巻、第１５１１頁（１９７４）。）そして熱
硬化性樹脂の分野において、耐熱性の向上を意図してア
セチレン基、ノルボルネン環、マレイミドとシアナート
の組み合わせ等の架橋基をもつ各種素材が開発されてい
る。2. Description of the Related Art In recent years, attention has been paid to the synthesis of a single crystal polymer using a topochemical reaction by solid-state polymerization, and using this technique, attempts have been made to develop highly crystalline polymers having various high elastic moduli. Has been. (For example, “Organic Nonlinear Optical Materials”, CMC (1985), Macromolecular Chemistry, Vol. 134, p. 219 (197).
0), Journal of Polymer Science B
9, Vol. 133 (1971), Journal of Polymer Science, Polymer Physics Edition, Vol. 12, 1511 (1974). ) In the field of thermosetting resins, various materials having a cross-linking group such as an acetylene group, a norbornene ring, and a combination of maleimide and cyanate have been developed for the purpose of improving heat resistance.
【０００３】[0003]
【発明が解決しようとする課題】しかし、これらの新規
な架橋基は、反応温度が高く、また成形時間がかかる等
の欠点がある。従って、架橋反応を十分に行なわせ、良
好な成形体を得るためには過酷な成形条件が要求され
る。本発明者らは、反応性の高い官能基としてジアセチ
レン基に着目し、架橋基としての特性を検討してきた。
その結果、１つの分子内にジアセチレン基と二重結合が
含有された素材が、硬化反応性に優れた素材であること
を見い出し、更に鋭意検討の結果、本発明に至った。However, these novel crosslinking groups have drawbacks such as high reaction temperature and long molding time. Therefore, severe molding conditions are required to sufficiently carry out the crosslinking reaction and obtain a good molded product. The present inventors have paid attention to a diacetylene group as a highly reactive functional group, and have investigated the properties as a crosslinking group.
As a result, they have found that a material containing a diacetylene group and a double bond in one molecule is a material having excellent curing reactivity, and as a result of further earnest studies, the present invention was achieved.
【０００４】[0004]
【問題点を解決するための手段】すなわち、本発明は、[Means for Solving the Problems] That is, the present invention is
【０００５】[0005]
【化２】 [Chemical 2]
【０００６】繰り返し単位として、式（１）の構造を有
し、数平均重合度が２〜２００である二重結合を有する
ジアセチレン重合体（ここで、Ａは炭素−炭素二重結合
を有する２価の炭化水素基、Ｒ1 ，Ｒ2 は２価の有機基
を表わす。）を提供するものである。本発明において、
Ｒ1 ，Ｒ2 は、同種又は異種の２価の有機基であり、そ
の例としては、A diacetylene polymer having a double bond having a structure of the formula (1) as a repeating unit and having a number average degree of polymerization of 2 to 200 (wherein A has a carbon-carbon double bond). A divalent hydrocarbon group, R 1 and R 2 represent a divalent organic group.). In the present invention,
R 1 and R 2 are the same or different divalent organic groups, and examples thereof include
【０００７】[0007]
【化３】 [Chemical 3]
【０００８】等の芳香族基、脂肪族基、及び脂環式基の
複合した基が挙げられ、またこれらのＲ1 ，Ｒ2 中の水
素原子のいくつかが、ハロゲン原子、ニトロ基、水酸
基、シアノ基、カルボキシル基、アミノ基、アミド基、
エステル基、カルボニル基、エーテル結合等で、置換さ
れていてもよい。また、当該有機基は、エーテル結合、
スルホニル結合、エステル結合、カルボニル結合等で結
ばれてなる有機基でも良く、この具体例を挙げるなら
ば、Examples thereof include a composite group of an aromatic group, an aliphatic group, and an alicyclic group. Some of the hydrogen atoms in R 1 and R 2 are halogen atoms, nitro groups, and hydroxyl groups. , Cyano group, carboxyl group, amino group, amide group,
It may be substituted with an ester group, a carbonyl group, an ether bond or the like. Further, the organic group is an ether bond,
An organic group formed by a sulfonyl bond, an ester bond, a carbonyl bond or the like may be used.
【０００９】[0009]
【化４】 [Chemical 4]
【００１０】等がある。これらのＲ1 ，Ｒ2 のうち好ま
しいのは、合成のしやすさと耐熱性の良さから、Etc. Of these R 1 and R 2 , preferred are those that are easy to synthesize and have good heat resistance.
【００１１】[0011]
【化５】 [Chemical 5]
【００１２】が好ましい。本発明における炭素−炭素二
重結合を有する炭化水素基Ａは、一般に炭素数２〜２０
の２価の炭化水素基であり、その例としては、Is preferred. The hydrocarbon group A having a carbon-carbon double bond in the present invention generally has 2 to 20 carbon atoms.
Is a divalent hydrocarbon group of, for example,
【００１３】[0013]
【化６】 [Chemical 6]
【００１４】等の炭素−炭素二重結合と水素原子又は、
脂肪族基の組合せで構成された基、A carbon-carbon double bond such as and a hydrogen atom, or
A group composed of a combination of aliphatic groups,
【００１５】[0015]
【化７】 [Chemical 7]
【００１６】等の炭素−炭素二重結合が環構造中に含ま
れる基等が挙げられる。これら炭化水素基の水素原子の
うちいくつかが、ニトロ基、水酸基、シアノ基、カルボ
キシル基、アミノ基、ハロゲン原子等で置換されていて
もよい。これらの炭素−炭素二重結合を有する炭化水素
基Ａの中で好ましいものは、硬化反応性からExamples thereof include groups in which a carbon-carbon double bond is contained in the ring structure. Some of the hydrogen atoms of these hydrocarbon groups may be substituted with a nitro group, a hydroxyl group, a cyano group, a carboxyl group, an amino group, a halogen atom or the like. Among these hydrocarbon groups A having a carbon-carbon double bond, the preferable one is the curing reactivity.
【００１７】[0017]
【化８】 [Chemical 8]
【００１８】等である。本発明のジアセチレン重合体
は、数平均重合度が２〜２００であり、オリゴマー、更
にはポリマーであってもよく、また、共重合体の一部で
あってもよい。本発明のジアセチレン重合体の具体例と
しては、以下の繰り返し単位を持つオリゴマー、ポリマ
ー等が挙げられる。And so on. The diacetylene polymer of the present invention has a number average degree of polymerization of 2 to 200, and may be an oligomer, a polymer, or a part of a copolymer. Specific examples of the diacetylene polymer of the present invention include oligomers and polymers having the following repeating units.
【００１９】[0019]
【化９】 [Chemical 9]
【００２０】本発明のジアセチレン重合体を合成するに
は既知の有機合成反応を応用改良して合成することがで
きる。例えば、２官能の塩化シアル基を持った化合物In order to synthesize the diacetylene polymer of the present invention, the known organic synthetic reaction can be applied and improved to synthesize. For example, a compound having a bifunctional sialic chloride group
【００２１】[0021]
【化１０】 [Chemical 10]
【００２２】と、末端にエチニル基を持つアルコール
（例えばＨＣ≡Ｃ−ＣＨ2 −ＯＨ）を２当量反応させる
ことで、両末端にエチニル基を持つエステル化合物And an alcohol having an ethynyl group at the ends (for example, HC≡C--CH 2 --OH) are reacted in an amount of 2 equivalents to give an ester compound having an ethynyl group at both ends.
【００２３】[0023]
【化１１】 [Chemical 11]
【００２４】が得られるので、これを酸化カップリング
反応させれば、ジアセチレン結合を含有した高分子量体
を合成できる。又、あらかじめ酸化カップリング反応で
合成したジアセチレン化合物（例えば、ＨＯ−ＣＨ2 −
Ｃ≡Ｃ−Ｃ≡Ｃ−ＣＨ2 −ＯＨ）と二重結合を有する化
合物Since ## STR1 ## is obtained, a high molecular weight compound containing a diacetylene bond can be synthesized by subjecting this to an oxidative coupling reaction. Further, diacetylene compound synthesized in advance oxidative coupling reaction (e.g., HO-CH 2 -
C≡C-C≡C-CH 2 -OH) and a compound having a double bond
【００２５】[0025]
【化１２】 [Chemical 12]
【００２６】を縮合反応させる方法も利用できる。この
酸化カップリング反応において用いる金属触媒のモル数
は基質に対し０．０１〜１当量、酸素の流量は１０〜１
０００ｍｌ／分が好ましい。この反応に用いる溶媒とし
てはピリジンが好ましいが、他の溶媒を共存させること
も可能である。反応温度、反応時間についても特に制限
はないが、好ましくは、反応温度は−２０〜１００℃の
間であり、反応時間は２０分から１２時間の範囲であ
る。A method in which the condensation reaction of The number of moles of the metal catalyst used in this oxidative coupling reaction is 0.01 to 1 equivalent to the substrate, and the flow rate of oxygen is 10 to 1
000 ml / min is preferred. Pyridine is preferred as the solvent used in this reaction, but it is also possible to coexist with other solvents. The reaction temperature and the reaction time are not particularly limited, but the reaction temperature is preferably between -20 and 100 ° C, and the reaction time is in the range of 20 minutes to 12 hours.
【００２７】[0027]
【発明の効果】本発明のジアセチレン重合体は、ジアセ
チレン基と炭素−炭素二重結合の組合せにより、硬化反
応性に優れ、また硬化物が良好な耐熱性及び機械物性を
発現する。本発明のジアセチレン化合物は、これらの特
性を生かし、高度な剛性や耐熱性及び硬化反応性を要求
される電子部品や精密機械部品の分野に利用できる。The diacetylene polymer of the present invention has excellent curing reactivity due to the combination of the diacetylene group and the carbon-carbon double bond, and the cured product exhibits good heat resistance and mechanical properties. The diacetylene compound of the present invention can be utilized in the fields of electronic parts and precision machine parts, which are required to have high rigidity, heat resistance and curing reactivity by making use of these characteristics.
【００２８】[0028]
【実施例】次に本発明を実施例により具体的に説明す
る。EXAMPLES Next, the present invention will be specifically described by way of examples.
【００２９】[0029]
【実施例１】[Example 1]
【００３０】[0030]
【化１３】 [Chemical 13]
【００３１】プロパルギルアルコールとフマル酸クロリ
ドをジメチルアニリンの存在下で反応させて、ＨＣ≡Ｃ
ＣＨ2 ＯＯＣＣＨ＝ＣＨＣＯＯ−ＣＨ2 Ｃ≡ＣＨを合成
した。得られたＨＣ≡ＣＣＨ2 ＯＯＣＣＨ＝ＣＨＣＯＯ
ＣＨ2 Ｃ≡ＣＨ １．０ｍｏｌをピリジン２００ｍｌを
溶媒として、塩化第１銅０．１ｍｏｌの存在下で、酸素
をバブリングして反応させ、目的物を得た。 ＩＲ：２９５０ｃｍ-1、２２００ｃｍ-1、１７５０ｃｍ
-1 、１２９０ｃｍ-1２２００ｃｍ-1の末端ＨＣ≡Ｃ−
から数平均重合度を求めたところ、２．８であった。こ
の重合体は、１６０℃で容易に硬化する。Propargyl alcohol and fumaric acid chloride are reacted in the presence of dimethylaniline to give HC≡C.
It was synthesized CH 2 OOCCH = CHCOO-CH 2 C≡CH. Obtained HC≡CCH 2 OOCCH = CHCOO
1.0 mol of CH 2 C≡CH was used as a solvent in 200 ml of pyridine as a solvent, and bubbling oxygen in the presence of 0.1 mol of cuprous chloride to cause a reaction to obtain the desired product. IR: 2950 cm -1 , 2200 cm -1 , 1750 cm
-1 , 1,290 cm -1 2200 cm -1 terminal HC ≡ C-
The number average degree of polymerization was determined from 2.8. The polymer cures easily at 160 ° C.
【００３２】[0032]
【実施例２】Example 2
【００３３】[0033]
【化１４】 [Chemical 14]
【００３４】蒸留精製したクロロベンゼンとｏ−ジクロ
ルベンゼンを容積比８０：２０の割合に混ぜた２００ｍ
ｌの溶媒に200 m in which chlorobenzene purified by distillation and o-dichlorobenzene were mixed in a volume ratio of 80:20.
l solvent
【００３５】[0035]
【化１５】 [Chemical 15]
【００３６】を加え、激しく撹拌した（３０分）。反応
後、大量のエタノールに反応物を注ぎ、析出した重合体
を単離した。ＧＰＣによる数平均重合度は、１９２であ
った。Was added and stirred vigorously (30 minutes). After the reaction, the reaction product was poured into a large amount of ethanol, and the precipitated polymer was isolated. The number average degree of polymerization by GPC was 192.
【００３７】[0037]
【実施例３】Example 3
【００３８】[0038]
【化１６】 [Chemical 16]
【００３９】を用いた以外は、実施例２を繰り返した。 ＩＲ：１７４６ｃｍ-1、１２８４ｃｍ-1 ＧＰＣによる数平均重合度は、９７であった。この重合
体は、１３０℃で容易に硬化する。Example 2 was repeated except that was used. IR: The number average degree of polymerization by 1746 cm -1 and 1284 cm -1 GPC was 97. The polymer cures easily at 130 ° C.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 徳重 健作 宮崎県延岡市旭町６丁目4100番地 旭化成 工業株式会社内 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Kensaku Tokushige 6-4100 Asahi-cho, Nobeoka-shi, Miyazaki Prefecture Asahi Kasei Kogyo Co., Ltd.
Claims (1)
合度が２〜２００である二重結合を有するジアセチレン
重合体（ここで、Ａは炭素−炭素二重結合を有する２価
の炭化水素基、Ｒ1 ，Ｒ2 は２価の有機基を表わす）。Claims: As a repeating unit, a diacetylene polymer having a structure of formula (1) and a double bond having a number average degree of polymerization of 2 to 200 (wherein A is a divalent carbon-carbon double bond). A hydrocarbon group, R 1 and R 2 represent a divalent organic group).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33384792A JPH0693092A (en) | 1992-12-14 | 1992-11-20 | Diacetylenic polymer having double bond |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33384792A JPH0693092A (en) | 1992-12-14 | 1992-11-20 | Diacetylenic polymer having double bond |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24151586A Division JPS6396144A (en) | 1986-10-13 | 1986-10-13 | Diacetylene compound having double bond |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0693092A true JPH0693092A (en) | 1994-04-05 |
Family
ID=18270616
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33384792A Pending JPH0693092A (en) | 1992-12-14 | 1992-11-20 | Diacetylenic polymer having double bond |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0693092A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5475133A (en) * | 1994-11-28 | 1995-12-12 | The Regents Of The University Of California | Bis-propargyl thermosets |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6396144A (en) * | 1986-10-13 | 1988-04-27 | Agency Of Ind Science & Technol | Diacetylene compound having double bond |
-
1992
- 1992-11-20 JP JP33384792A patent/JPH0693092A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6396144A (en) * | 1986-10-13 | 1988-04-27 | Agency Of Ind Science & Technol | Diacetylene compound having double bond |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5475133A (en) * | 1994-11-28 | 1995-12-12 | The Regents Of The University Of California | Bis-propargyl thermosets |
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