JPH0469358A - Asymmetric diacetylene compound - Google Patents
Asymmetric diacetylene compoundInfo
- Publication number
- JPH0469358A JPH0469358A JP17950190A JP17950190A JPH0469358A JP H0469358 A JPH0469358 A JP H0469358A JP 17950190 A JP17950190 A JP 17950190A JP 17950190 A JP17950190 A JP 17950190A JP H0469358 A JPH0469358 A JP H0469358A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- asymmetric
- expressed
- diacetylene
- diacetylene 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.)
- Pending
Links
- -1 diacetylene compound Chemical class 0.000 title claims abstract description 22
- 150000002430 hydrocarbons Chemical group 0.000 claims abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 abstract description 9
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 150000002148 esters Chemical class 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- 230000001588 bifunctional effect Effects 0.000 abstract 1
- 239000012320 chlorinating reagent Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000009257 reactivity Effects 0.000 description 9
- 238000000862 absorption spectrum Methods 0.000 description 8
- 238000004587 chromatography analysis Methods 0.000 description 6
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000001237 Raman spectrum Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- LLCSWKVOHICRDD-UHFFFAOYSA-N buta-1,3-diyne Chemical group C#CC#C LLCSWKVOHICRDD-UHFFFAOYSA-N 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 230000000269 nucleophilic effect Effects 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- OSFBJERFMQCEQY-UHFFFAOYSA-N propylidene Chemical compound [CH]CC OSFBJERFMQCEQY-UHFFFAOYSA-N 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OGFAWKRXZLGJSK-UHFFFAOYSA-N 1-(2,4-dihydroxyphenyl)-2-(4-nitrophenyl)ethanone Chemical compound OC1=CC(O)=CC=C1C(=O)CC1=CC=C([N+]([O-])=O)C=C1 OGFAWKRXZLGJSK-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000013598 vector Substances 0.000 description 1
Landscapes
- 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〕
本発明は非対称ジアセチレン化合物に関するものであり
、更に詳しくは分子末端の一方に、求核反応性、あるい
は求電子反応性に富んだ反応部位を有する非対称ジアセ
チレン化合物に関するものである。[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to an asymmetric diacetylene compound, and more specifically, a reactive site rich in nucleophilic reactivity or electrophilic reactivity at one end of the molecule. This relates to an asymmetric diacetylene compound having the following.
線状高分子の配向による一軸方向への高弾性率化は、ア
ルミニウムやスチールを凌ぐレベルに到達している。一
方、熱硬化性樹脂に代表される等方性材料の高弾性率化
は、はとんど試みられていなかった。このような背景の
中で、本発明者らはジアセチレン基と炭素−炭素不飽和
結合を有する化合物を用いた高弾性率材料の開発を行な
ってきた。（例えば、特開昭６３−１４５３３７号公報
、特開昭６３−２９５６１２号公報）。The high modulus of elasticity in the uniaxial direction due to the orientation of linear polymers has reached a level that surpasses that of aluminum and steel. On the other hand, no attempt has been made to increase the elastic modulus of isotropic materials such as thermosetting resins. Against this background, the present inventors have been developing a high elastic modulus material using a compound having a diacetylene group and a carbon-carbon unsaturated bond. (For example, JP-A-63-145337, JP-A-63-295612).
本発明者らによって開発されてきた高弾性率ジアセチレ
ン系架橋体は、等方的に１０ＧＰａ以上、架橋条件や分
子構造の最適化により２０ＧＰａ以上の弾性率を発現す
る。このような高弾性率化は架橋密度の増大によって達
成されたが、架橋密度を高めることによって得られた架
橋体は脆くなり、ある程度の強度が要求される用途によ
っては使用上問題となった。タフネスを上げるためには
架橋密度を下げなければいけないが、単にモノマーの架
橋基を減らすような試みは架橋体の弾性率も低下させて
しまう。弾性率を低下させずに高タフネスを有する架橋
体を製造しようとする試みやそれを現実させうる概念は
皆無であった。The high modulus diacetylene crosslinked product developed by the present inventors exhibits an elastic modulus of 10 GPa or more isotropically, and 20 GPa or more by optimizing the crosslinking conditions and molecular structure. Such a high modulus of elasticity was achieved by increasing the crosslink density, but the crosslinked body obtained by increasing the crosslink density became brittle, which caused problems in use depending on the application where a certain degree of strength was required. In order to increase toughness, it is necessary to lower the crosslinking density, but attempts to simply reduce the number of crosslinking groups in the monomer will also lower the elastic modulus of the crosslinked product. There have been no attempts to produce a crosslinked body with high toughness without lowering the elastic modulus, or any concept that could make this a reality.
本発明は、高タフネスを有する架橋体を与えるジアセチ
レン系ポリマーの合成に有用な非対称ジアセチレン化合
物を提供することを目的とする。An object of the present invention is to provide an asymmetric diacetylene compound useful in the synthesis of a diacetylene polymer that provides a crosslinked product with high toughness.
タフネスを向上させるには架橋点間の距離をできるだけ
長くする必要がある。そこで、側鎖に反応性官能基を有
するポリマーと分子末端の一方に求核反応性、あるいは
求電子反応性に富んだ非対称ジアセチレン化合物を反応
させると、得られたポリマーがタフネスを持つ高弾性率
材料になり得る可能性を見出した。更に、本発明者らは
、その非対称ジアセチレン化合物の分子構造や反応性を
総括的に検討した結果、本発明に到達した。即ち、本発
明は、一般式（１）で示される非対称ジアセチレン化合
物である。To improve toughness, it is necessary to make the distance between crosslinking points as long as possible. Therefore, by reacting a polymer having a reactive functional group in its side chain with an asymmetric diacetylene compound rich in nucleophilic reactivity or electrophilic reactivity at one end of the molecule, the resulting polymer has toughness and high elasticity. We found the possibility that it could be used as a rate material. Furthermore, the present inventors comprehensively studied the molecular structure and reactivity of the asymmetric diacetylene compound, and as a result, they arrived at the present invention. That is, the present invention is an asymmetric diacetylene compound represented by general formula (1).
ｙ−ｃｏｏ−Ｒ−ｃ＝ｃｃ＝ｃ−Ｒ’−ｘ −−−
（１）（ここで、Ｙは炭素数２から６までの不飽和結合
を有する１価の炭化水素基を示し、Ｒ，Ｒ’は炭素数１
から６までの２価の炭化水素基を示し、Ｘは０Ｈ１−Ｎ
Ｈ，、−ＣＩ、−Ｂｒから選ばれた基を示す。）本発明
において、Ｙは炭素数が２〜６までの不飽和結合を有す
る１価の炭化水素基を示し、その具体例としては、
−ＣＨ＝ＣＨ２、−Ｃ（ＣＨ３）−ＣＨ２、−ＣＨ＝Ｃ
ＨＣＨ３、ＣＨ＝Ｃ（ＣＬ）２、−ＣＨ＝ＣＨＣＨ２Ｃ
Ｈ３、−ＣＨ＝ＣＨＣＨ２ＣＨ３、ＣＨ２ＣＨ＝ＣＨＣ
Ｈ３、−ＣＨ２ＣＨ２ＣＨ＝ＣＨＣＨ２ＣＨ３、Ｃ＝Ｃ
Ｈ１−ＣミＣＣＨ３、−ＣＨ２Ｃ−＝ ＣＣＨ２ＣＨ３
等が挙げられる。これらのＹのうち、高弾性率化を達成
しやすい点では−ＣＨ＝ＣＨ２、−Ｃ（ＣＨ３）＝Ｃ１
（、。y-coo-R-c=cc=c-R'-x ---
(1) (Here, Y represents a monovalent hydrocarbon group having 2 to 6 carbon atoms and having an unsaturated bond, and R and R' have 1 carbon number.
represents a divalent hydrocarbon group from to 6, and X is 0H1-N
It represents a group selected from H,, -CI, and -Br. ) In the present invention, Y represents a monovalent hydrocarbon group having 2 to 6 carbon atoms and an unsaturated bond, and specific examples thereof include -CH=CH2, -C(CH3)-CH2, -CH =C
HCH3, CH=C(CL)2, -CH=CHCH2C
H3, -CH=CHCH2CH3, CH2CH=CHC
H3, -CH2CH2CH=CHCH2CH3, C=C
H1-CmiCCH3, -CH2C-=CCH2CH3
etc. Among these Y, -CH=CH2, -C(CH3)=C1 are easy to achieve high elastic modulus.
(,.
−Ｃ＝ＣＨが好ましく、特にその効果が顕著な点から−
ＣＨ＝ＣＨ２、’Ｃ（ＣＨ３）二ＣＨ２が好ましい。-C=CH is preferred, especially since its effect is remarkable -
CH=CH2, 'C(CH3)2CH2 is preferred.
Ｒ，Ｒ’は炭素数が１から６までの２価の炭化水素基を
示し、その具体例としては、
ＣＨ２Ｃ２Ｈ４Ｃ３Ｈ６Ｃ４Ｈ３−
ＣＨ（ＣＨ３）−−Ｃ（ＣＨ３）２− か挙げられる。R and R' represent a divalent hydrocarbon group having 1 to 6 carbon atoms, and specific examples include CH2C2H4C3H6C4H3- CH(CH3)--C(CH3)2-.
これらのＲ，Ｒ’のうち、架橋体の弾性率の大きさＸは
一０Ｈ１−ＮＨ２、−ＣＩ２、−Ｂｒ から選ばれた
基を示す。−０Ｈ１−Ｎｌ（２は、求電子性官能基と、
また−ＣＩ！、−Ｂｒは求核性官能基と高い反応性を有
しているので、例えば、高分子反応に本発明の非対称ジ
アセチレン化合物を用いる場合、反応相手のポリマーの
側鎖の反応性によってその使い分けをすれば良い。特に
、反応性の良さからは、−ＮＨ２、Ｂｒが好ましく、合
成の収率の良さや操作のしやすさからは、−０Ｈ１−Ｃ
Ｉが好ましい。Among these R and R', the magnitude X of the elastic modulus of the crosslinked body represents a group selected from -0H1-NH2, -CI2, and -Br. -0H1-Nl (2 is an electrophilic functional group,
Again - CI! , -Br has high reactivity with nucleophilic functional groups, so for example, when using the asymmetric diacetylene compound of the present invention in a polymer reaction, its use can be determined depending on the reactivity of the side chain of the polymer to be reacted with. All you have to do is In particular, from the viewpoint of good reactivity, -NH2 and Br are preferable, and from the viewpoint of good synthesis yield and ease of operation, -0H1-C
I is preferred.
本発明の非対称ジアセチレン化合物の具体例を示すなら
ば以下のようなものが挙げられる。Specific examples of the asymmetric diacetylene compound of the present invention include the following.
ＣＨ２＝ＣＨＣ００ＣＨ２Ｃ；−ＣいＣＣＨ２０ＨＣＨ
２＝ＣＨＣＯＯＣＨ２Ｃ−：ＣいＣＣＨ，ＮＨ２ＣＨ２
＝ＣＨＣＯＯＣＨ２いＣいＣＣＨ２ＣｆｆＣＩ（ｚ”ｃ
ＨｃＯＯｃＨ２Ｃ’ＣＣ””ＣＣＨ２０ＨＣＨ３
ＣＨ２”ＣＣ００ＣＨ２０ＣいＣＣＨ２０ＨＣＨ。CH2=CHC00CH2C;-CCH20HCH
2=CHCOOCH2C-:CCH,NH2CH2
=CHCOOCH2CCH2CffCI(z”c
HcOOcH2C'CC""CCH20HCH3 CH2"CC00CH20CCCH20HCH.
ＣＨ２”ＣＣ００ＣＨ２Ｃ′：ＣＣ’ＣＣ８２Ｎ！（２
Ｈ３
ＣＨ２＝ＣＣＯＯＣＨ２昨ＣいＣＣＨ２０ＨＣＨ３
ＣＨ２”ＣＣ００ＣＨ２Ｃ’ＣＣ’ＣＣＨ２ＢｒＣｌ−
１２＝Ｃ）（ＣＯＯ＋いＣいＣＣＨ２０ＨＣＨ２”ＣＨ
ＣＯＯ舎いＣ区÷ＮＨ２
ＣＨ２二ＣＨＣＯＯＣＨ２Ｃ−ＣＯヱｃ＋ ｃβｃＨ２
＝ｃ＋−＋ｃｏｏ４→ＣＣ’Ｃ（シＢｒＨＣ″′−ＣＣ
ＯＯＣＨ２いＣ昨ＣＣＨ２０ＨＣＨ２＝ＣＨＣＯＯ（Ｃ
Ｈ２）２昨Ｃ宸Ｃ（ＣＨ２）２０ＨＣＨ２・ＣＨＣＯＯ
（ＣＬ ）２叶Ｃ宸Ｃ（ＣＨ２）２ｃｊ２ＣＨ２・ＣＨ
ＣＯＯ（ＣＨ２） ２昨ＣＣ−＝Ｃ（ＣＨ２）２ＢｒＣ
Ｈ２・ＣＨＣＯＯ（ＣＨ２）２いＣいＣ（ＣＨ２）２Ｎ
Ｈ２本発明の非対称ジアセチレン化合物は一般式的な有
機合成法を適用することにより容易に合成できる。従っ
て、特定の合成方法に限定されるものではない。CH2"CC00CH2C':CC'CC82N!(2
H3 CH2=CCOOCH2CCH20HCH3 CH2"CC00CH2C'CC'CCH2BrCl-
12=C) (COO+CCH20HCH2”CH
COO building C section ÷ NH2 CH22CHCOOCH2C-COec+ cβcH2
=c+-+coo4→CC'C(BrHC″'-CC
OOCH2C lastCCH20HCH2=CHCOO(C
H2) 2 last time C (CH2) 20HCH2・CHCOO
(CL) 2 leaves C shin C (CH2) 2cj2CH2・CH
COO(CH2) 2 last CC-=C(CH2)2BrC
H2・CHCOO(CH2)2CicC(CH2)2N
H2 The asymmetric diacetylene compound of the present invention can be easily synthesized by applying general organic synthesis methods. Therefore, it is not limited to a specific synthesis method.
典型的な合成例を挙げると以下のような方法が考えられ
る。Typical synthesis examples include the following methods.
ＹＣＯＯ）１． ＋ ＨＯＲいＣいＣＲ”ＯＨ→ＹＣＯ
ＯＲいＣいＣＲＯＨ（２）
（２） →ＹＣＯＯＲＣ＝ＣいＣＲＮＨ２（２）
→ＹＣＯＯＲＣ；′″−ＣいＣＲＣｊ２（２） →Ｙ
ＣＯＯＲ〉ｃｃ’ｃＲＢｒカルボン酸ＹＣＯＯＨとジア
セチレンジオールＨＯＲＣ＝ＣＣ： ＣＲＯＨを常法の
エステル化反応によってハーフエステル（２）が得られ
る。エステル化の具体的な方法は、例えば、モリリン、
ボイド著” 有機科学（上）、（中）、（下）”東京化
学同人、第３版に記載されている方法がそのまま適用で
きる。この合成反応においてはカルボン酸とジアセチレ
ンジオールの仕込比のバランスを崩してジエステルの生
成をできるだけ押えることが重要である。カボン酸とジ
アセチレンジオールの仕込比（モル比）は、−船釣には
、ｌＯ／１〜ｌ／１０であり、収率の点から好ましくは
３／１〜１／３、特に好ましくは２／１−１／２である
。また、いずれの仕込比においても反応物は原料やジエ
ステルを含むので、（２）を単離するために、クロマト
処理や再結晶、蒸留などの精製手段をとることかでき、
むしろそのような精製手段をとることは好ましい。この
エステル化反応にはカルボン酸の代りにカルボン酸クロ
リドを用いても良い。YCOO)1. + HOR ICR”OH→YCO
ORICROH(2) (2) →YCOORC=CCRNH2(2)
→YCOORC；′″-CCRCj2(2) →Y
COOR〉cc'cRBrCarboxylic acid YCOOH and diacetylene diol HORC=CC: Half ester (2) is obtained by esterifying CROH in a conventional manner. Specific methods of esterification include, for example, Moririn,
The method described in "Organic Science (Part 1), (Middle), (Part 2)" by Boyd, Tokyo Kagaku Doujin, 3rd edition can be applied as is. In this synthesis reaction, it is important to suppress the production of diester as much as possible by unbalancing the charging ratio of carboxylic acid and diacetylene diol. The charging ratio (molar ratio) of carboxylic acid and diacetylene diol is -10/1 to 1/10 for boat fishing, preferably 3/1 to 1/3, particularly preferably 2 /1-1/2. In addition, since the reactants contain raw materials and diesters at any charging ratio, purification methods such as chromatography, recrystallization, and distillation can be used to isolate (2).
Rather, it is preferable to use such a purification method. In this esterification reaction, carboxylic acid chloride may be used instead of carboxylic acid.
（２）は、アンモニアなどのアミン化試薬、塩化チオニ
ル、三塩化リン、五塩化リンなどのクロル化試薬、三臭
化リン、五臭化リンなどのブロモ化試薬と反応させるこ
とにより対応するＹＣＯＯＲＣ：ＣＣ＝ＣＲＮＨ２、Ｙ
ＣＯＯＲＣ＝ ＣＣ＝ ＣＲＣｌ 、 ＹＣＯＯＲＣ＝
ＣＣ＝ ＣＲＢｒに容易に変換できる。具体的な変換
方法は、例えば、モリリン、ボイド著”有機科学（上）
、（中）、（下）”東京化学同人、第３版に記載されて
いる方法がそのまま適用できる。得られたこれらの非対
称ジアセチレン化合物についても、クロマト処理や再結
晶、蒸留などの精製手段をとることができ、むしろその
ような精製手段をとることは好ましい。(2) can be obtained by reacting with an amination reagent such as ammonia, a chlorination reagent such as thionyl chloride, phosphorus trichloride, or phosphorus pentachloride, or a bromination reagent such as phosphorus tribromide or phosphorus pentabromide. :CC=CRNH2,Y
COORC= CC= CRCl, YCOORC=
It can be easily converted to CC=CRBr. For specific conversion methods, see "Organic Science (Part 1)" by Moririn and Boyd.
, (Middle), (Bottom) The method described in "Tokyo Kagaku Doujin, 3rd edition" can be applied as is. These asymmetric diacetylene compounds obtained can also be purified by purification methods such as chromatography, recrystallization, and distillation. However, it is preferable to use such a purification method.
得られた非対称ジアセチレン化合物の構造は、ＮＭＲス
ペクトル、赤外吸収スペクトル、紫外及び可視吸収スペ
クトル、ラマンスペクトル、マススペクトル、元素分析
、Ｘ線回折、クロマトグラフィーなどの分析手段によっ
て同定できる。The structure of the obtained asymmetric diacetylene compound can be identified by analytical means such as NMR spectrum, infrared absorption spectrum, ultraviolet and visible absorption spectrum, Raman spectrum, mass spectrum, elemental analysis, X-ray diffraction, and chromatography.
以下、実施例を挙げて本発明をより具体的に説明するか
、言うまでもなく、実施例のみに本発明が限定されるも
のではない。Hereinafter, the present invention will be explained in more detail with reference to Examples, but it goes without saying that the present invention is not limited to the Examples.
実施例１
ジアセチレンジオール（ＨＯＲＣ門ＣＣ＝ＣＲＯＨ）
０．１モルとカルボン酸クロリド（ＹＣＯＣＡ ） ０
１）モルを精製ジオキサン３０−とＮ−メチルピロリド
ン１〇−の混合溶媒中、６０℃にて３時間反応させた。Example 1 Diacetylene diol (HORC phylum CC=CROH)
0.1 mol and carboxylic acid chloride (YCOCA) 0
1) Moles were reacted at 60° C. for 3 hours in a mixed solvent of 30-years of purified dioxane and 10-years of N-methylpyrrolidone.
反応後、溶媒を留去し、得られた反応物をエーテルに溶
解した後、希水酸化ナトリウム水溶液と水で洗浄した。After the reaction, the solvent was distilled off, and the resulting reaction product was dissolved in ether and washed with dilute aqueous sodium hydroxide solution and water.
ポウ硝で乾燥後、このエーテル溶液を濃縮し反応物をシ
リカゲルカラム処理した。その結果を第１表に示す。After drying with sulfuric acid, the ether solution was concentrated and the reaction product was treated with a silica gel column. The results are shown in Table 1.
同定は、ＮＭＲスペクトル、赤外吸収スペクトル、紫外
及び可視吸収スペクトル、ラマンスペクトル、マススペ
クトル、元素分析、Ｘ線回折、クロマトグラフィーなど
を用いて行なった。Identification was performed using NMR spectra, infrared absorption spectra, ultraviolet and visible absorption spectra, Raman spectra, mass spectra, elemental analysis, X-ray diffraction, chromatography, and the like.
実施例２
実施例１で得られたアルコール０．１モルをピリジン３
０−に□溶解し、この溶液に塩化チオニルを１０７１Ｌ
ｌを２時間かけて、５℃を越えないようにして滴下した
。滴下終了後、４０℃まで昇温し、更に１時間撹拌した
。反応後、反応物をエーテルに溶解した後、希水酸化ナ
トリウム水溶液と水で洗浄した。ボウ硝で乾燥後、この
エーテル溶液を濃縮し反応物をシリカゲルカラム処理し
た。その結果を第２表に示す。Example 2 0.1 mol of the alcohol obtained in Example 1 was added to 3 mol of pyridine.
0-, and add 1071 L of thionyl chloride to this solution.
1 was added dropwise over 2 hours without exceeding 5°C. After the dropwise addition was completed, the temperature was raised to 40°C, and the mixture was further stirred for 1 hour. After the reaction, the reaction product was dissolved in ether and washed with dilute aqueous sodium hydroxide solution and water. After drying with glass salt, the ether solution was concentrated and the reaction product was treated with a silica gel column. The results are shown in Table 2.
同定は、ＮＭＲスペクトル、赤外吸収スペクトル、紫外
及び可視吸収スペクトル、ラマンスペクトル、マスクベ
クトル、元素分析、Ｘ線回折、クロマトグラフィーなど
を用いて行なった。Identification was performed using NMR spectra, infrared absorption spectra, ultraviolet and visible absorption spectra, Raman spectra, mask vectors, elemental analysis, X-ray diffraction, chromatography, and the like.
実施例３
実施例２において、塩化チオニルの代りに、三臭化リン
を用いた以外は、実施例２を繰返した。Example 3 Example 2 was repeated except that phosphorus tribromide was used instead of thionyl chloride.
得られた結果は、第３表に示す。The results obtained are shown in Table 3.
実施例４
実施例２又は、３で得られた非対称ジアセチレン化合物
０．１モルをテトラヒドロフラン２０１ｎｌに容解し、
この溶液に濃アンモニア水２０−を加え、３０８Ｃにて
２４時間反応させた。反応後、溶媒を留去し、得られた
残渣をエーテルに溶解した。このエーテル溶液を希塩酸
水で洗浄した。塩酸層を分離し、希水酸化ナトリウム水
溶液を用いてアルカリ処理した後、エーテル抽出した。Example 4 0.1 mol of the asymmetric diacetylene compound obtained in Example 2 or 3 was dissolved in 201 nl of tetrahydrofuran,
To this solution was added 20 mm of concentrated ammonia water, and the mixture was reacted at 308C for 24 hours. After the reaction, the solvent was distilled off, and the resulting residue was dissolved in ether. This ether solution was washed with diluted hydrochloric acid water. The hydrochloric acid layer was separated, treated with alkali using dilute aqueous sodium hydroxide solution, and then extracted with ether.
ボウ硝で乾燥後、このエーテル溶液を濃縮し反応物をシ
リカゲルカラム処理した。その結果を第４表に示す。After drying with glass salt, the ether solution was concentrated and the reaction product was treated with a silica gel column. The results are shown in Table 4.
同定は、ＮＭＲスペクトル、赤外吸収スペクトル、紫外
及び可視吸収スペクトル、ラマンスペクトル、マススペ
クトル、元素分析、Ｘ線回折、クロマトグラフィーなど
を用いて行なった。Identification was performed using NMR spectra, infrared absorption spectra, ultraviolet and visible absorption spectra, Raman spectra, mass spectra, elemental analysis, X-ray diffraction, chromatography, and the like.
比較のために、同じ条件で５．７−トデカジイン１，１
２−ジオール ジアクリレート及び５，７−ドデカジイ
ン−１，１２−ジオール ジメタクリレートを硬化させ
て得られた硬化物の物性を測定したところ、弾性率は各
々７．８ ＧＰａと７．０ＧＰａであったかその強度は
８０ＭＰａ程度であった。For comparison, 5,7-todecadiine 1,1 under the same conditions
When the physical properties of the cured products obtained by curing 2-diol diacrylate and 5,7-dodecadiyne-1,12-diol dimethacrylate were measured, the elastic modulus was 7.8 GPa and 7.0 GPa, respectively. The strength was about 80 MPa.
この結果は、本発明の非対称ジアセチレン化合物を用い
た架橋体が弾性率とタフ、ネスに優れていることを示す
ものである。This result shows that the crosslinked product using the asymmetric diacetylene compound of the present invention is excellent in elastic modulus, toughness, and ness.
本発明の非対称ジアセチレン化合物は、側鎖に反応性官
能基を有するポリマーと極めて効率的に高分子反応し、
架橋反応性に富んだポリマーを与える。得られた架橋体
は、高弾性率の他に、タフネスも兼ね備えている。従っ
て、本発明の非対称ジアセチレン化合物は、等方的な高
強度、高弾性率材料の原料として有用である。The asymmetric diacetylene compound of the present invention reacts extremely efficiently with a polymer having a reactive functional group in its side chain,
Provides a polymer with high crosslinking reactivity. The obtained crosslinked body has not only high elastic modulus but also toughness. Therefore, the asymmetric diacetylene compound of the present invention is useful as a raw material for isotropic high-strength, high-modulus materials.
特許出願人 旭化成工業株式会社Patent applicant: Asahi Kasei Industries, Ltd.
Claims (1)
。 Ｙ−ＣＯＯ−Ｒ−Ｃ≡ＣＣ≡Ｃ−Ｒ′−Ｘ・・・・・・
・・（１）（ここで、Ｙは炭素数２から６までの不飽和
結合を有する１価の炭化水素基を示し、Ｒ、Ｒ′は炭素
数１から６までの２価の炭化水素基を示し、Ｘは−ＯＨ
、−ＮＨ＿２、−Ｃｌ、−Ｂｒから選ばれた基を示す。 ）[Claims] 1. An asymmetric diacetylene compound represented by general formula (1). Y-COO-R-C≡CC≡C-R'-X...
...(1) (Here, Y represents a monovalent hydrocarbon group having 2 to 6 carbon atoms and an unsaturated bond, and R and R' are divalent hydrocarbon groups having 1 to 6 carbon atoms. and X is -OH
, -NH_2, -Cl, -Br. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17950190A JPH0469358A (en) | 1990-07-09 | 1990-07-09 | Asymmetric diacetylene compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17950190A JPH0469358A (en) | 1990-07-09 | 1990-07-09 | Asymmetric diacetylene compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0469358A true JPH0469358A (en) | 1992-03-04 |
Family
ID=16066922
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17950190A Pending JPH0469358A (en) | 1990-07-09 | 1990-07-09 | Asymmetric diacetylene compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0469358A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5848553A (en) * | 1996-02-16 | 1998-12-15 | Asmo Co., Ltd. | Motor device |
| US5855140A (en) * | 1996-02-19 | 1999-01-05 | Asmo Co. Ltd. | Motor device |
| US6963007B2 (en) * | 2002-12-19 | 2005-11-08 | 3M Innovative Properties Company | Diacetylenic materials for sensing applications |
| US7364918B2 (en) | 2002-12-19 | 2008-04-29 | 3M Innovative Properties Company | Colorimetric sensors constructed of diacetylene materials |
-
1990
- 1990-07-09 JP JP17950190A patent/JPH0469358A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5848553A (en) * | 1996-02-16 | 1998-12-15 | Asmo Co., Ltd. | Motor device |
| US5855140A (en) * | 1996-02-19 | 1999-01-05 | Asmo Co. Ltd. | Motor device |
| US6963007B2 (en) * | 2002-12-19 | 2005-11-08 | 3M Innovative Properties Company | Diacetylenic materials for sensing applications |
| US7364918B2 (en) | 2002-12-19 | 2008-04-29 | 3M Innovative Properties Company | Colorimetric sensors constructed of diacetylene materials |
| US7816473B2 (en) * | 2002-12-19 | 2010-10-19 | 3M Innovative Properties Company | Diacetylenic materials for sensing applications |
| US8063164B2 (en) | 2002-12-19 | 2011-11-22 | 3M Innovative Properties Company | Diacetylenic materials for sensing applications |
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