JPH01106852A - Diacetylene amide containing double bond - Google Patents
Diacetylene amide containing double bondInfo
- Publication number
- JPH01106852A JPH01106852A JP26371787A JP26371787A JPH01106852A JP H01106852 A JPH01106852 A JP H01106852A JP 26371787 A JP26371787 A JP 26371787A JP 26371787 A JP26371787 A JP 26371787A JP H01106852 A JPH01106852 A JP H01106852A
- Authority
- JP
- Japan
- Prior art keywords
- diacetylene
- double bond
- groups
- formula
- compound
- 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.)
- Granted
Links
- -1 Diacetylene amide Chemical class 0.000 title claims description 12
- 125000000962 organic group Chemical group 0.000 claims abstract description 7
- LLCSWKVOHICRDD-UHFFFAOYSA-N buta-1,3-diyne Chemical group C#CC#C LLCSWKVOHICRDD-UHFFFAOYSA-N 0.000 abstract description 17
- 239000003054 catalyst Substances 0.000 abstract description 7
- 230000009257 reactivity Effects 0.000 abstract description 7
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 4
- 238000005691 oxidative coupling reaction Methods 0.000 abstract description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 3
- 239000004020 conductor Substances 0.000 abstract description 3
- 239000010949 copper Substances 0.000 abstract description 3
- 229910001882 dioxygen Inorganic materials 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 abstract description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052802 copper Inorganic materials 0.000 abstract description 2
- 239000012766 organic filler Substances 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 1
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 abstract 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract 1
- 229910017052 cobalt Inorganic materials 0.000 abstract 1
- 239000010941 cobalt Substances 0.000 abstract 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract 1
- 238000004132 cross linking Methods 0.000 abstract 1
- 229910052748 manganese Inorganic materials 0.000 abstract 1
- 239000011572 manganese Substances 0.000 abstract 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 125000003368 amide group Chemical group 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004455 differential thermal analysis Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- JKANAVGODYYCQF-UHFFFAOYSA-N prop-2-yn-1-amine Chemical compound NCC#C JKANAVGODYYCQF-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 1
- JXYITCJMBRETQX-UHFFFAOYSA-N 4-ethynylaniline Chemical compound NC1=CC=C(C#C)C=C1 JXYITCJMBRETQX-UHFFFAOYSA-N 0.000 description 1
- 238000006590 Cadiot-Chodkiewicz coupling reaction Methods 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 102100038239 Protein Churchill Human genes 0.000 description 1
- 238000003436 Schotten-Baumann reaction Methods 0.000 description 1
- 150000004703 alkoxides Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- JGJLWPGRMCADHB-UHFFFAOYSA-N hypobromite Inorganic materials Br[O-] JGJLWPGRMCADHB-UHFFFAOYSA-N 0.000 description 1
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Inorganic materials Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/52—Amides or imides
- C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F20/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、二重結合含有ジアセチレンアミドに関するも
のであり、更に詳しくは、二重結合が高い反応性を有し
二重結合とジアセチレン基を独立に固相反応させること
により、網目状高分子を与えうる二重結合含有ジアセチ
レンアミドに関するものである。Detailed Description of the Invention [Industrial Application Field] The present invention relates to a double bond-containing diacetylene amide, and more specifically, the double bond has high reactivity and the double bond and diacetylene amide This invention relates to a double bond-containing diacetylene amide that can give a network polymer by subjecting the groups to a solid phase reaction independently.
近年、ジアセチレン化合物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
を用いて導電性材料、光学素子、記録材料、そして高弾
性率を有する機能性材料の開発が試みられている。In recent years, the synthesis of single-crystal polymers using topochemical reactions with diacetylene compounds has attracted attention, and attempts have been made to use this method to develop conductive materials, optical elements, recording materials, and functional materials with high elastic modulus. It is being
本発明者らも、すでにアミド基、エステル基、イミド基
等を有する新規なジアセチレン化合物を合成し、これら
を用いた高弾性率高分子成形体の開発を行ってきた。The present inventors have already synthesized novel diacetylene compounds having amide groups, ester groups, imide groups, etc., and have been developing high-modulus polymer molded articles using these.
特に、炭素−炭素二重結合とジアセチレン基を組み合せ
ることによって弾性率をより一層高めうろことも見い出
してきた。In particular, it has been discovered that scales have even higher elastic modulus by combining carbon-carbon double bonds and diacetylene groups.
〔発明が解決しようとしている問題点〕しかしながら、
これまでに開発されてきた式（１）のような二重結合含
有ジアセチレン化合物では、・・・・・・式（１）
（Ａ、Ａ”は、二重結合を有する一価の有機基、Ｒ，Ｒ
’ は、２価の有機基を示す。）Ａ、Ａ’ とＲ，Ｒ’
の組合せによっては、ジアセチレン基及び／又は、二
重結合の反応性が極度に小さくなり、網目状高分子（ジ
アセチレン基と二重結合が独立に反応し、網目状の分子
構造を有する高分子）は、生成し難く、未反応の二重結
合やジアセチレン基が数多く残ったり、たとえ得られた
としてもその製造条件が、著しく厳しい場合がある。例
えば、ＡやＲを立体的に大きくしすぎたりすると、ジア
セチレン基の反応性が低下し、二重結合しか反応しない
場合がある。しかしながらＡ、Ｒを立体的に小さくしす
ぎると逆の減少が生じてしまう。又Ａ、Ｒの立体的効果
のみならず、その誘起的効果、二重結合の位置や結合様
式等、効果的に網目状高分子を得るには、これらの諸問
題をすべて解決しなければならない。[Problem that the invention is trying to solve] However,
In the double bond-containing diacetylene compounds such as the formula (1) that have been developed so far,...Formula (1) (A, A'' are monovalent organic groups having a double bond) ,R,R
' represents a divalent organic group. ) A, A' and R, R'
Depending on the combination of molecules) are difficult to produce, many unreacted double bonds and diacetylene groups remain, and even if they are obtained, the manufacturing conditions may be extremely harsh. For example, if A or R is made too sterically large, the reactivity of the diacetylene group may decrease and only double bonds may react. However, if A and R are made too small sterically, the opposite decrease will occur. Furthermore, in order to effectively obtain a network polymer, it is necessary to solve all of these problems, including not only the steric effects of A and R, but also their inductive effects, the positions and bonding styles of double bonds, etc. .
本発明者らは、上記の問題を解決するために、二重結合
とジアセチレン基との反応性を比較検討し、二重結合と
ジアセチレン基を独立して反応せしめ、且つ網目状高分
子を与えうる条件を探索する過程において ｌ）二重結
合が、α−β不飽和アミド型になっていること ２）二
重結合の置換基の炭素数が３より小さく、直線状には３
個の炭素が並ばないようになっていること、又、アミド
基とジアセチレン基との連結基Ｒ，Ｒ”ができるだけ立
体的に小さいこと、の３点が効率良く網目状高分子を得
る上で大切であることを見い出した。さらに、アミド基
、ジアセチレン基、二重結合との結合様式、及び各官能
基の間に入る有機基の有無並びにその種類等を鋭意研究
の結果、本発明に到達した。In order to solve the above-mentioned problems, the present inventors conducted a comparative study on the reactivity between double bonds and diacetylene groups, reacted the double bonds and diacetylene groups independently, and created a network polymer. In the process of searching for conditions that could give
In order to efficiently obtain a network polymer, three points are necessary: the carbon atoms are not lined up, and the linking groups R and R'' between the amide group and the diacetylene group are sterically as small as possible. Furthermore, as a result of intensive research into the bonding mode with amide groups, diacetylene groups, and double bonds, as well as the presence or absence of organic groups interposed between each functional group and their types, the present invention was discovered. reached.
すなわち、本発明は
Ｉ
Ｘ ＸＣＨ２である
二重結合含有ジアセチレンアミド（ここで、Ｘは水素原
子又はメチル基、Ｒ，Ｒ″は炭素数が１から６までの２
価の有機基を示す。）を提供するものである。That is, the present invention relates to a double bond-containing diacetylene amide that is I
Indicates a valent organic group. ).
本発明において、Ｘは水素原子又はメチル基である。こ
の場合、二重結合の反応性を高めるには水素原子の方が
好ましく、ジアセチレン基と二重結合との反応をバラン
スさせるにはメチル基の方が好ましい。In the present invention, X is a hydrogen atom or a methyl group. In this case, a hydrogen atom is preferable in order to increase the reactivity of the double bond, and a methyl group is preferable in order to balance the reaction between the diacetylene group and the double bond.
一方、Ｒ，Ｒ“は炭素数が１から６までの２価の有機基
であり、その例としては、−ＣＯ，−。On the other hand, R and R'' are divalent organic groups having 1 to 6 carbon atoms, examples of which include -CO, -.
ＣＨ３
Ｃ１１２ＣＨＣＩＩＺ 、 ＣＨ２ＣＨ２ＣＨ２Ｃ
Ｈ２、Ｃ１１２ＣＨ２ＣＨ２ＣＩＩ□Ｃ）！、−。CH3 C112CHCIIZ, CH2CH2CH2C
H2, C112CH2CH2CII□C)! ,-.
これらの２価の有機１４Ｒ，Ｒ’ 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
ルボニル基、アミノ基、アミド基、エステル基、アルコ
キシド基等で置換されていてもよい。Even if some of the hydrogen atoms of these divalent organic 14R, R' are substituted with halogen atoms, nitro groups, hydroxyl groups, cyano groups, carbonyl groups, amino groups, amide groups, ester groups, alkoxide groups, etc. good.
これらのＲ，Ｒ’ のうちジアセチレン基の反応性しく
、合成のしやすさ等を考えると、−ＣＨ２−が特に好ま
しい。Among these R and R', -CH2- is particularly preferred in view of the reactivity of the diacetylene group and the ease of synthesis.
本発明の二重結合含有ジアセチレンアミドの合成法の例
としては、Ｒ＝Ｒ’ のとき、支
ような金属触媒と酸素ガスを用いて酸化カッブリソゲさ
せることにより合成できる（Ｇ Ｉ ａ ｓ ｅ ｒカ
ップリング）。As an example of the method for synthesizing the double bond-containing diacetylene amide of the present invention, when R=R', it can be synthesized by oxidation oxidation using a supporting metal catalyst and oxygen gas (G I a se r Coupling).
一方、Ｒｆ＝Ｒ’ のとき、
支
ハロゲン化してから、酢酸銅のような金属触媒を支
カップリングすることにより合成できる（Ｃａｄｉｏｔ
−Ｃｈｏｄｋｉｅｗｉｃｚ反応）。On the other hand, when Rf=R', it can be synthesized by supporting halogenation and then supporting coupling with a metal catalyst such as copper acetate (Cadiot
- Chodkiewicz reaction).
上記合成例において、酸化カップリング反応の触媒とし
ては、銅、マンガン、コバルト塩を用いることができ、
必要に応じて３級アミン、オキシム等の助触媒を共存さ
せてもよい。金属塩としては、ＣｕＣｌ、 ＣｕＣ１ｚ
＋ Ｃｕｂ、 Ｃｕ（ＯＯＣＣＨｓ）ｚ１ＭｎＣ１ｚ＋
ＭｎＣＯ３＋ ＣｏＣ［ｚを用いることができる。In the above synthesis example, copper, manganese, and cobalt salts can be used as catalysts for the oxidative coupling reaction,
If necessary, a co-catalyst such as a tertiary amine or oxime may be present. As metal salts, CuCl, CuClz
+ Cub, Cu (OOCCHs)z1MnC1z+
MnCO3+ CoC[z can be used.
上記の合成例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、１０〜１０００ＩＩ１１／ ｒｎｉｎが好ま
しい。In the oxidative coupling reaction of the above synthesis example, the number of moles of the metal catalyst used is preferably 0.01 to 1 equivalent relative to the substrate, and the flow rate of oxygen is preferably 10 to 1000 II11/rnin.
この反応に用いる溶媒としては特に制限はなく、例えば
ピリジン、アセトン、メタノール等が挙げられ、他の第
二の溶媒を共存させてもよい。反応時間、反応温度につ
いては特に制限はないが、好ましくは反応時間は１０分
から１２時間、反応温度は−２０”Ｃから１００’Ｃの
間である。The solvent used in this reaction is not particularly limited, and examples thereof include pyridine, acetone, methanol, etc., and other second solvents may also be present. There are no particular limitations on the reaction time and reaction temperature, but preferably the reaction time is 10 minutes to 12 hours and the reaction temperature is between -20''C and 100'C.
上記合成例において
支
素をハロゲン化する場合、常法に従って、次亜塩素酸ア
ルカリ金属塩、次亜臭素酸アルカリ金属塩せればよい。In the case of halogenating the supporting element in the above synthesis example, an alkali metal hypochlorite or an alkali metal hypobromite may be converted according to a conventional method.
支
を常法のショツテン−バウマン反応させることにより大
量かつきわめて容易に合成できる。It can be synthesized in large quantities and extremely easily by carrying out the conventional Schotten-Baumann reaction.
本発明の二重結合含有ジアセチレンアミドは、高い反応
性を有するジアセチレン化合物であり、ジアセチレン基
と二重結合を独立に反応させることにより高架橋密度を
有する網目状高分子を与える。The double bond-containing diacetylene amide of the present invention is a diacetylene compound having high reactivity, and provides a network polymer having a high crosslink density by reacting diacetylene groups and double bonds independently.
特に得られた網目状高分子が、単結晶又は結晶性が高い
場合、有機フィラー、光学材料、導電性材料の原料とし
て有用である。In particular, when the obtained network polymer is single crystal or has high crystallinity, it is useful as a raw material for organic fillers, optical materials, and conductive materials.
（実施例〕
以下に、本発明の実施例を挙げるが、本発明は以下の実
施例に限定されるものではない。(Examples) Examples of the present invention are listed below, but the present invention is not limited to the following examples.
□〔実施例１〕
０．１モルのプロパルギルアミンと０．１モルのＮａＯ
Ｈを含む５０ｍ１の水を、０．１モルのアクリル酸クロ
リドを含む３００ｍ１のクロロホルム溶液に、０〜５°
Ｃで、１時間かけて滴下した。滴下後、さらに１０分間
、１０°Ｃにて撹拌し、クロロホルム層を分離、濃縮し
て
＋１Ｈ
ＣＨｚ−ＣＨＣＮＣＨｚＣ＝ＣＨを得た。□ [Example 1] 0.1 mol of propargylamine and 0.1 mol of NaO
50 ml of water containing H was added to 300 ml of chloroform solution containing 0.1 mol of acrylic acid chloride at 0-5°C.
C, and was added dropwise over 1 hour. After the dropwise addition, the mixture was further stirred at 10°C for 10 minutes, and the chloroform layer was separated and concentrated to obtain +1H CHz-CHCNCHzC=CH.
＋１Ｈ
次いで、ＣＩ□＝ＣＨＣＮＧＨｚＣ＝ＣＩ ０．０１
モル、ＣｕＣ１Ｏ，００５モルを２０ｍｌ１のビリジン
ニ溶かし、酸素ガスを導入しながら、室温ｔ２時間反応
させた。+1H Then CI□=CHCNGHzC=CI 0.01
1,005 moles of CuClO were dissolved in 20 ml of pyridine, and the mixture was reacted at room temperature for 2 hours while introducing oxygen gas.
反応後、析出した目的物を吸引ろ過にて単離した。After the reaction, the precipitated target product was isolated by suction filtration.
得られた目的物の総数率は５６％であった。The total number of target products obtained was 56%.
Ｉ Ｒ（Ｋ Ｂ ｒ ） ３２３８ｃｙ＋＋−
’、 ３０５０ｃｍ−’、 １６５１ｃｍ −区。I R (K B r ) 3238cy++-
', 3050cm-', 1651cm-ku.
１６２４−’、 １５４０ｃｍ−’、 １２４５ｃｍ−
’上記のアミド化合物をメタノールより再結晶し、アル
ゴン中、１７０’Ｃで５時間、アニーリングすると、定
量的にポリマー（赤かっ色）ができた。このポリマーの
ＩＲスペクトル、ラマンスペクトルより、二重結合とジ
アセチレン基はほとんど残存していないことが明らかと
なった。例えば、アニーリング前には１６２４− ’の
Ｃ＝Ｃに基づく伸縮振動があるが、ポリマーにはそのピ
ークは、みられなかった。1624-', 1540cm-', 1245cm-
'The above amide compound was recrystallized from methanol and annealed in argon at 170'C for 5 hours, yielding a quantitative polymer (reddish brown). The IR spectrum and Raman spectrum of this polymer revealed that almost no double bonds and diacetylene groups remained. For example, there is a stretching vibration based on C=C of 1624-' before annealing, but no such peak was observed in the polymer.
１１）！
一方、（ＣｆｌＺ＝ＣＨＣＨ□ＣＨ２ＣＮＣＨ２Ｃ：Ｃ
→２゜Ｃ＋Ｚ
等のジアセチレン化合物を、ＴＧ−ＤＴＡ （熱重量−
示差熱分析）で調べた分解点までの温度範囲で、熱、光
等の励起手段を用いて重合を試みたが、処理後ＩＲスペ
クトル、ラマンスペクトルより、ジアセチレン基、及び
二重結合ともにその半分も反応しなかった。11)! On the other hand, (CflZ=CHCH□CH2CNCH2C:C
→ Diacetylene compounds such as 2゜C+Z are converted into TG-DTA (thermogravimetric -
Polymerization was attempted using excitation means such as heat and light in the temperature range up to the decomposition point determined by differential thermal analysis (differential thermal analysis), but after treatment, IR spectra and Raman spectra showed that both diacetylene groups and double bonds were lost. Not even half of them responded.
〔実施例２］
アクリル酸クロリドの代わりに、メタクリル酵クロリド
を用いた以外は実施例１を繰り返した。[Example 2] Example 1 was repeated except that methacrylic acid chloride was used instead of acrylic acid chloride.
得られた目的物の総酸率は、６２％であった。The total acidity of the obtained target product was 62%.
Ｉ Ｒ（Ｋ Ｂ ｒ ） ３２３８ｃｍ−’、 ３０４
８ｃｍ−’、 ２９８３ｃｍ−’。I R (K B r ) 3238 cm-', 304
8cm-', 2983cm-'.
１６５４ＣＩＩ＋−’、 １６２０Ｃ１＋１−’、 １
５４０印−１プロパルギルアミンの代ワリにＨＣ＝Ｃ（
ＣＨｚ）Ｊｔｌ□を用いた以外は実施例１を繰り返した
。1654CII+-', 1620C1+1-', 1
540 mark - HC=C (
Example 1 was repeated except that Jtl□ (Chz)Jtl□ was used.
得られた目的物の総酸率は、８６％であった。The total acidity of the obtained target product was 86%.
Ｅ Ｒ（Ｋ Ｂ ｒ ） ３２３８ｃｍ−’＋ ３（１
４８ｃｍ−’、 ２９６４ｃｍ−’。E R (K B r ) 3238 cm-'+ 3 (1
48cm-', 2964cm-'.
１６５５ｃｍ−’、 １６１０ｃｍ−’、 １５４０ｃ
ｍ−’プロパルギルアミンの代わりに、Ｐ−エチニルア
ニリンを用いた以外は実施例１を繰り返した。1655cm-', 1610cm-', 1540c
Example 1 was repeated except that P-ethynylaniline was used instead of m-'propargylamine.
得られた目的物の総酸率は、９２％であった。The total acidity of the obtained target product was 92%.
Ｉ Ｒ（Ｋ Ｂ ｒ ） ３２４０ｃｍ−’、 ３００
８ｃｍ−’、 １６２８ｃｍ−’。I R (K B r ) 3240 cm-', 300
8cm-', 1628cm-'.
１５９８ｃｒｎ−’、 １５３６ｃｍ−’〔実施例５］
アクリル酸クロリド０．１モルと、
０．１モルのトリエチルアミン存在下１００ｄの四塩化
炭素中、３時間Ｏ″Ｃにて反応させた。反応後、溶媒を
留去し、くり返しエタノールで残香を洗うことにより目
的物を単離した。1598 crn-', 1536 cm-' [Example 5] 0.1 mol of acrylic acid chloride was reacted with 0.1 mol of triethylamine in 100 d of carbon tetrachloride for 3 hours at O''C. After the reaction, The target product was isolated by distilling off the solvent and repeatedly washing the residual aroma with ethanol.
得られた目的物の収率は、はぼ定量的であった。The yield of the target product obtained was almost quantitative.
Ｉ Ｒ（Ｋ Ｂ ｒ ） ３２３６ｃｍ−’、 ３０１
０ｃｍ−’、 １６１８ｃｍ−’。I R (K B r ) 3236 cm-', 301
0cm-', 1618cm-'.
Claims (1)
数が１から６までの２価の有機基を示す。）[Claims] A double bond-containing diacetylene amide whose structural formula is ▲ Numerical formula, chemical formula, table, etc. (Indicates divalent organic groups up to 6.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26371787A JPH01106852A (en) | 1987-10-21 | 1987-10-21 | Diacetylene amide containing double bond |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26371787A JPH01106852A (en) | 1987-10-21 | 1987-10-21 | Diacetylene amide containing double bond |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01106852A true JPH01106852A (en) | 1989-04-24 |
| JPH0525874B2 JPH0525874B2 (en) | 1993-04-14 |
Family
ID=17393334
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26371787A Granted JPH01106852A (en) | 1987-10-21 | 1987-10-21 | Diacetylene amide containing double bond |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01106852A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0337213A (en) * | 1989-07-04 | 1991-02-18 | Asahi Chem Ind Co Ltd | Diacetylene composition |
-
1987
- 1987-10-21 JP JP26371787A patent/JPH01106852A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0337213A (en) * | 1989-07-04 | 1991-02-18 | Asahi Chem Ind Co Ltd | Diacetylene composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0525874B2 (en) | 1993-04-14 |
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