JPH0576937B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a butadiinamide dimer and a crosslinked product thereof, and more specifically, a butadiinamide dimer and a crosslinked product thereof that can be used as a raw material for a polymer having an extremely highly crystalline network structure. It is related to. [Prior art and its problems] The present inventors have developed a high elastic modulus molded product by three-dimensionally or two-dimensionally crosslinking it with high density using a compound having a diacetylene group. Until now, various functional butadiyne compounds have been synthesized. In order to express a high elastic modulus three-dimensionally by crosslinking using covalent bonds, the crosslinking group density must be made as high as possible and the crosslinking groups must be reacted regularly and in high yield. The present inventors have hitherto found that without impairing the chemical stability of the compound,
Butadiyne compounds, which have a high density of crosslinking groups and high reactivity of the crosslinking groups, are made possible by combining amide groups or ester groups with diacetylene groups or carbon-carbon double bonds, and these materials can be used to form solid phase compounds. We have achieved high elastic modulus using reactions. However, the regularity of the reaction was still insufficient. That is, since the structure is disordered during the crosslinking reaction, phenomena such as an increase in the peak of the amorphous portion are observed in, for example, X-ray diffraction, and as a result, there is a limit to further improvement of the elastic modulus. If the reaction does not proceed regularly, the diacetylene groups gradually become unable to react in the solid phase, resulting in problems such as unreacted diacetylene groups remaining. On the other hand, research to obtain a highly regular network structure by combining diacetylene groups and triple bonds is
JB in Synth, Met, vol. 9, p. 314 (1984).
As also seen in the report by Lando et al., these materials (e.g., HC≡C( _CH2 ) ₈ C≡CC≡C--
(CH ₂ ) ₈ C≡CH) has a long and flexible linking group connected between the diacetylene group and the triple bond, and the molecular design is such that this linking group absorbs the strain during the reaction process. ing. However, due to the long linking group, the density of the crosslinking group decreases, which is far from achieving the high-density crosslinking that the present inventors are aiming for. In addition, in this case, it has been reported that if a short linking group is used to increase the density of the crosslinking group, the crystallinity will be significantly reduced (Hachiro Nakanishi 4th Next Generation Industrial Infrastructure Technology Symposium, High Crystallization (September 1986). [Means for Solving the Problems] Based on the above knowledge, the present inventors have intensively studied the relationship between the main types of linking groups, regularity, and reactivity, and as a result, the inventors have found the following in the claims: The present invention was achieved by discovering that amide compounds generally have high reactivity, and that diacetylene groups and terminal double bonds have high regular solid phase reactivity. That is, the present invention provides the following features: 1) The structural formula is substantially

[C] (Here, A is -CH ₂ - or

[Formula] B is −CH ₂ −, (—CH ₂ ) ₂ —, (—CH ₂ ) ₃ —, (—CH ₂ ) ₄ —,
(-CH ₂ ) ₅ --, (-CH ₂ ) ₆ --,

【formula】

【formula】

[Formula] is a hydrocarbon group selected from -CH=CH-, -CH ₂ CH= CHCH ₂ -, -CH ₂ C≡CCH ₂ -. ) and a crosslinked product of the butadiinamide dimer. In the present invention, A is _-CH2- or

[Formula], to improve the reactivity of the terminal triple bond and increase the crosslink density, -CH ₂ -, and to improve the heat resistance

[Formula] is preferred. In the present invention, B is -CH ₂ -, (-CH ₂ ) ₂ --,
(-CH ₂ ) ₃ --, (-CH ₂ ) ₄ --, (-CH ₂ ) ₅ --
, (-CH ₂
) ₆ ---,

【formula】 【formula】

[Formula] − CH=CH−, −CH ₂ CH=CHCH ₂ −, −CH ₂ C≡
It is a hydrocarbon group selected from CCH ₂ -, etc. In order to increase the crosslinking group density, −CH ₂ −, −CH ₂ CH ₂ −, −
CH=CH- is preferable, as it is a planar functional group that increases the reactivity of the diacetylene group.

[Formula] -CH=CH- is preferred, and -CH=CH- is particularly preferred. As a method for synthesizing the butadiinamide dimer of the present invention, for example, diamide

[Formula] -C≡ Can be synthesized by subjecting CH to an oxidative coupling reaction.
In this case, not only dimers but also trimers, tetramers, or oligomers with a higher degree of polymerization may be produced, but by lowering the polarity of the reaction solvent, dimers can be mainly produced in the reaction system with high selectivity. It is possible to precipitate from As a method for extracting only the dimer from the precipitated compound, it can be isolated by conventional methods such as liquid chromatography and recrystallization. As the oxidation coupling method, the so-called Glaser coupling method can be applied, and dimerization is performed using a metal catalyst and oxygen gas. Copper, manganese, cobalt salts, etc. can be used as catalysts for the oxidized katupurin reaction, and if necessary, co-catalysts such as tertiary amines and oximes may be present. For example, as a catalyst, CuCl,
CuCl ₂ , CuI ₂ , Cu(OOCCH ₃ ) ₂ , MnCl ₂ ,
MnCO ₃ , CoCl ₂ and the like can be used. In the oxidative coupling reaction, the number of moles of the metal catalyst used is 0.01 to 1 equivalent per mole of diamide as a substrate, and the flow rate of oxygen is 0.01 to 1 equivalent per mole of substrate diamide.
The rate is preferably 10 to 1000 ml/min, but there is no particular restriction. Examples of the solvent used in the reaction include pyridine, acetone, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethylsulfoxide, and other second solvents may also be present. There are no particular restrictions on the reaction temperature and reaction time, but preferably the reaction temperature is -20°C to 100°C,
Reaction time is 10 minutes to 12 hours. Furthermore, diamide

【ceremony,

〔Effect of the invention〕

Although the butadiyne dimer of the present invention has a short flexible linking group, both the diacetylene group and the terminal triple bond have high reaction regularity during the crosslinking process. Therefore, the amide crosslinked product of the present invention has a highly crystalline and dense network structure, and can be used as a high modulus resin for bases, precision equipment parts, structural materials, etc. When the body is whisker-shaped, it is also useful as a reinforcing material for composite materials. [Example] Examples are given below, but the present invention is not limited to the following examples. Example 1

Synthesis of [Formula] and production of its crosslinked product Dissolve 0.1 mole of dipropargyl fumaramide synthesized from propargylamine and fumaric acid chloride in 200 ml of a mixed solvent of pyridine:N-methylpyrrolidone = 2:1, and add copper chloride () to the solution. 0.01 mol was added, and the mixture was stirred at room temperature for 5 hours while blowing oxygen gas. After the reaction, the precipitated white solid was filtered and
After repeated recrystallization from N,N-dimethylacetamide, the desired product was obtained in a yield of 52%. The obtained amide dimer was identified by ¹ H-NMR, IR, Mass,
This was done by elemental analysis. The amide dimer thus obtained was 6500Kg/
When treated under pressure at 150°C ^for 1 hour, the diacetylene group and the terminal triple bond reacted almost quantitatively, yielding a red crosslinked product. When the amide dimer was formed into a disk shape of 2 mm thick and 10 mm in diameter using a pelletizer for infrared spectroscopy, the same pressure treatment was applied to give a completely integrated pellet-like molded product.
These crosslinked products have approximately the same level of crystallinity as the monomer according to their X-ray diffraction, with 2θ=6, 11,
Sharp diffraction peaks were shown at 14, 20, and 24. When the Raman and infrared absorption spectra of the crosslinked product were measured, the absorption of the diacetylene group and the terminal triple bond had disappeared. On the other hand, the dimer was heated at 150 °C under a nitrogen stream at normal pressure.
Even after treatment at ℃ for 1 hour, the diacetylene group and the terminal triple bond reacted quantitatively, but the crystallinity was slightly decreased. When the dimer was irradiated with 35 MRad of gamma rays using cobalt-60 as a radiation source, only about 90% of the diacetylene groups were polymerized. This reactant is further
When heat treated at 150°C for 1 hour, the terminal triple bonds also reacted and a highly crystalline crosslinked product was obtained. Example 2

Synthesis of [Formula] and production of its crosslinked product Example 1 was repeated except that dipropargyl succinamide was used instead of dipropargyl fumaramide. The yield of the amide dimer obtained was 59%
It was hot. The amide dimer thus obtained was 6500Kg/
cm ² , by pressure treatment at 200℃ for 1 hour,
The diacetylene group and the terminal triple bond reacted almost quantitatively, and a highly crystalline crosslinked product was obtained. Example 3

[ka] synthesis and production of its crosslinked product instead of dipropargyl fumaramide

Example 1 was repeated except that [Chemical formula] was used. The yield of the amide dimer obtained was 76%. The amide dimer thus obtained was 6500Kg/
cm ² , by pressure treatment at 200℃ for 1 hour,
The diacetylene group and the terminal triple bond reacted, and a highly crystalline crosslinked product was obtained. Example 4

Synthesis of [chemical formula] and production of its crosslinked product Instead of dipropargyl fumaramide,

[Reference example]

An oligomer that can synthesize dipropargyl fumarate ester by the same coupling reaction as in Example 1 (the number average degree of polymerization determined by ¹ H=NMR is
It was 3.0. ) at 6500Kg/cm ² ×150℃ for 1 hour,
When subjected to pressure treatment, the diacetylene group and the terminal triple bond react almost quantitatively, but when examining X-ray diffraction, no sharp diffraction peaks were observed, indicating a significant decrease in crystallinity. It was done.

Claims (1)

[Scope of _Claims ] 1 _The structural formula is substantially [Chemical Formula] ( _where A is -CH ₂ - or [Formula] ₂ ) ₃ ---, (-CH ₂ ) ₄ ---,
(-CH ₂ ) ₅ --, (-CH ₂ ) ₆ --, [Formula] [Formula] [Formula] -CH=CH-, -CH ₂ CH= CHCH ₂ -, -CH ₂ C≡CCH ₂ - A hydrocarbon group selected from ) butadiinamide dimer. 2 The structural formula is substantially [formula] (where A is -CH ₂ - or [formula] B is -CH ₂ -, (-CH ₂ ) ₂ --, (-CH ₂ ) ₃ -- , (-CH ₂ ) ₄ ---,
(-CH ₂ ) ₅ --, (-CH ₂ ) ₆ --, [Formula] [Formula] [Formula] -CH=CH-, -CH ₂ CH= CHCH ₂ -, -CH ₂ C≡CCH ₂ - A hydrocarbon group selected from ) A cross-linked product of butadiinamide dimer.