JPH0366334B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to an amide imide compound having a diacetylene group that is easily crosslinked by the diacetylene group and has excellent moldability and heat resistance. [Prior Art] In recent years, the synthesis of single-crystalline polymers using topochemical reactions through solid-state polymerization has attracted attention, and attempts have been made to use this method to develop highly crystalline polymers with various nominal moduli. ing. (For example, "Organic Nonlinear Optical Materials", CMC (1985), Macromolecule Chemistry No. 134
Vol. 219 (1970), Journal of Polymer Science Vol. B9, p. 133 (1971), Journal of Polymer Science Polymer Physics Edition Vol. 12, p. 1511 (1974). ) [Problem to be solved by the invention] However, the polymers of diacetylene compounds that have been synthesized so far have been obtained by photochemically or thermally polymerizing raw material monomer powder or single crystals. Since many polymers themselves are insoluble in water and organic solvents, their processability after polymerization is extremely poor. In addition, the diacetylene compounds with topochemical polymerizability that have been synthesized and researched so far are limited to compounds and derivatives with hydroxyl groups such as HOCH ₂ C≡C-C≡CCH ₂ OH, which has hindered the progress of research. It was getting worse. On the other hand, in materials with nitrogen atoms introduced, the electronegativity and cohesive force of the nitrogen atoms can be utilized, and if the nitrogen atoms have -NH- bonds, the intermolecular force due to hydrogen bonds and the reactivity of the nitrogen atoms can be utilized. It is possible to strengthen the intermolecular interactions of diacetylene compounds and develop various derivatives, such as the possibility of utilizing topochemical reactions, and there are great expectations for the potential of topochemical reactions and their practical application. From this point of view, amide-imidized compounds having a diacetylene group are of great interest;
Hitherto, hardly any amide-imidized products exhibiting such topochemical reactivity and having a diacetylene group have been known. The present inventors have conventionally investigated methods for introducing various groups such as alkyl groups next to diacetylene groups, and the properties of the resulting compounds. They were successful, and as a result of further intensive research, they arrived at the present invention. [Means for Solving the Problems] That is, the present invention provides an amide-imidized product having a repeating unit represented by the structural formula () and having a number average degree of polymerization of 2 to 100. (Here, R ¹ and R ² are divalent hydrocarbon groups having 1 to 30 carbon atoms, and Z is a trivalent hydrocarbon group having 1 to 40 carbon atoms.) In the present invention, R ¹ and R ² is 2 with 1 to 30 carbon atoms
R ¹ and R ² may be different. Examples are −CH ₂ −, −
C ₂ H ₄ −, −C ₃ H ₆ −, −C ₄ H ₈ −, −C ₅ H ₁₀ −, −
C ₈ H ₁₆ −, −C ₁₀ H ₂₀ −, −C ₁₂ H ₂₄ −, −C ₂₀ H ₄₀ −,

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Aliphatic groups such as [Formula], and alicyclic groups,

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Aromatic compounds such as [formula] base, and

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Examples include complex groups of aromatic groups, aliphatic groups, and alicyclic groups such as [Formula], and some of the hydrogen atoms of these R ¹ and R ² are halogen atoms, nitro groups, hydroxyl groups, It may be substituted with cyano acid, carboxyl group, amino group, amide group, ester group, carbonyl group, alkoxy group, etc., and these may be repeated or combined, and these hydrocarbon groups However, it may be connected with another bonding group. Examples of bonding groups other than hydrocarbons include -O-, -
S-, -SO ₂ -, -CO-, -NH-, -NCH ₃ -, -
COO−, −CONH−,

[Formula] -NHCO- NH-, -N=N-, -HC=N-, etc., and these may be combined or repeated. From the viewpoint of ease of synthesis and topochemical properties, R ¹ and R ² are preferably -CH ₂ -,

[Formula] − C ₂ H ₄ −,

[Formula]. In the present invention, Z is a trivalent hydrocarbon group having 1 to 40 carbon atoms, and examples thereof include CHCH ₂ -,
CHCH ₂ CH ₂ −, CHCH ₂ CH ₂ CH−,

[Formula] CH (CH ₂ ) ₉ −, CH (CH ₂ ) ₁₃ −,

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[Formula] etc. mentioned,

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The hydrocarbon group may be connected by a functional group having a heteroatom, such as in the following formula. Further, some or all of the hydrogen atoms of the above divalent hydrocarbon group may be a halogen atom, a nitro group, a cyano group, a carboxyl group, an amide group, an ester group, a carbonyl group,
It may be substituted with an alkoxy group or the like. Among these trivalent hydrocarbon groups, preferred are:
Due to the ease of synthesis and reactivity,

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[Formula] etc. The present invention also includes copolymers of structural formula () and polymers having other repeating units. In that case, as a repeating unit other than structural formula (),
There is no particular restriction, but preferably amide, imide,
Repeating units such as amide imide, ester, and ether are preferably used. In such a copolymer, the amount of the structural formula () of the present invention is not particularly limited, but is preferably 1 mol % or more, particularly preferably 5 mol % or more. The number average degree of polymerization of the amide imide compound of the present invention is 2 to 100. The amic acid derivative having a diacetylene group, which is a precursor of the amide imidide of the present invention, can be synthesized by making effective use of known organic synthesis reactions. For example, the diaminodiacetylene compound H ₂ N-R ¹ -C≡C-C≡C-R ² -NH ₂ and

A method of reacting an acid anhydride represented by [Formula] in an amide solvent, H ₂ N-R ¹ -C
≡CH and

〔Effect of the invention〕

The diacetylene group-containing amide-imidized product of the present invention takes an extremely effective orientation between molecular chains due to the cohesive force caused by the heteroatoms to cause a solid phase reaction by the diacetylene group, and is easily crosslinked, resulting in high elasticity. express the rate. For example, the shaped amide imide compound having a diacetylene group according to the present invention has good mechanical properties (e.g. elastic modulus), and while general organic polymers have an elastic modulus of 1 to 3 GPa, the elastic modulus is 5 GPa. The above elastic modulus can be easily achieved. In addition, depending on the application, it can be used in various forms such as powder, lump, solution, and suspension, and it can also be used in inorganic and organic fibrous, powder, and flaky materials. It is also possible to use them in combination, or in combination with other curable resins, polymeric materials, colorants, stabilizing materials, etc. Further, the amide imide compound of the present invention has extremely good heat resistance. As described above, the diacetylene group-containing amide imidide of the present invention has good moldability, heat resistance,
It is a new material that has both high elasticity and high modulus, and is extremely useful in fields that require these properties. [Example] Reference example 1 Synthesis of H ₂ NCH ₂ -C≡C-C≡CH ₂ NH ₂ 0.2 mol and 4-chloroformyl-phthalic anhydride 0.1 mol were dissolved in 200 ml of N-methylpyrrolidone and heated in nitrogen at 80°C for 2 hours. and reacted. After the reaction, the reaction product was poured into water, and the precipitated polymer was isolated by suction filtration. The yield of the obtained polymer was quantitative. The number average degree of polymerization determined from the IR (film) 3270 cm ^-1 , 1640 cm ^-1 , 1600 cm ^-1 IR spectra was 20. Example 1 Synthesis of the polyamic acid of Reference Example 1 under a nitrogen stream
Heat treatment was performed at 300°C for 30 minutes. The yield of the obtained polymer was quantitative. The number average degree of polymerization of the polymer determined from the IR spectrum was 52. IR (Nujol) 3008cm ^-1 , 1738cm ^-1 , 1600cm ^-1 When this product was subjected to thermogravimetric analysis in air, it was found that there was no raw material up to 280°C, indicating good heat resistance. Reference example 2 Synthesis of _H2N - _CH2 -C≡C-C≡C- _CH2 - _NH2 in Reference Example 1 Example 1 was repeated except that . The yield of the obtained polymer was quantitative, and its number average degree of polymerization was 2. IR (film) 3300cm ^-1 , 3000cm ^-1 ,
1648cm ^-1 1600cm ^-1 Example 2 The method of Example 1 was repeated using the amic acid of Reference Example 2. (or in acetic anhydride at 120℃, 1
It may be heated for a period of time. ) The obtained number average degree of polymerization was 2. IR (Nujol) 3000cm ^-1 , 1728cm ^-1 , 1600cm ^-1 The thermogravimetric analysis of this product in air showed no weight loss up to 300°C, indicating good heat resistance. Reference example 3 Synthesis of In Reference Example 2 instead of Example 3 was repeated except that . The yield of the obtained polymer was quantitative, and its number average degree of polymerization was 32. IR (film) 3300cm ^-1 , 3000cm ^-1 , 1648cm ^-1 Example 3 Synthesis of Reference Example 3 The method of Example 1 was repeated using polyamic acid. The yield of the obtained polymer was quantitative, and its number average degree of polymerization was 84. IR (Nujol) 3000cm ^-1 , 1728cm ^-1 , 1600cm ^-1 When this product was subjected to thermogravimetric analysis in air, it was found that there was no weight loss up to 380°C and that it had good heat resistance. Reference Example 4 In Reference Example 1, H ₂ N-CH ₂ -C≡C-C≡C-CH ₂ -NH ₂ was further added to 0.16 mol.

Reference Example 1 was repeated except that 0.04 mol of [Formula] was added. The number average degree of polymerization of the obtained polymer was 85. Example 4 The method of Example 1 was repeated using the polyamic acid of Reference Example 4. The number average degree of polymerization of the obtained polymer was 100. IR (Nujol) 3000cm ^-1 , 1740cm ^-1 , 1603cm ^-1 Reference Example 5 In Reference Example 1, _H2N - _CH2- C≡C-C≡C- _CH2 - _NH2 was further added to 0.18 mol.

Reference Example 1 was repeated by adding 0.02 mol of [Formula]. The number average degree of polymerization of the obtained polymer was 60. IR (film) 3300 cm ^-1 , 3000 cm ^-1 , 1650 cm ^-1 Example 5 The method of Example 1 was repeated using the polyamic acid of Reference Example 5. The obtained polymer had a number average degree of polymerization of 74. IR (Nujol) 3000cm ^-1 , 1739cm ^-1 , 1600cm ^-1 .

Claims (1)

[Scope of Claims] 1. An amide-imidized product having a repeating unit represented by the structural formula () and having a number average degree of polymerization of 2 to 100. (Here, R ¹ and R ² are divalent hydrocarbon groups having 1 to 30 carbon atoms, and Z is a trivalent hydrocarbon group having 1 to 40 carbon atoms.)